INTRODUCTION: In this work, we propose an innovative application of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as a methodological approach for the chemical characterisation of black crusts on stone monuments, associated with traditional micro-morphological (optical and scanning electron microscopy) and infrared spectroscopic techniques (FTIR). METHODS: This new approach was tested on black crusts developing on two marble substrates, one, the columns of the San Cosimato cloister in Rome, and the other, a sculpture representing an angel, located in Pessano con Bornago, a small industrial town near Milan. DISCUSSION: The main aim of this study was to develop and test the reliability of the LA-ICP-MS analytical method on black crusts and to explore the idea that trace element concentrations in black crusts can be applied to investigate their origin and the relations between concentrations of polluting elements in black crusts and environmental conditions. CONCLUSION: The results obtained by applying traditional techniques find considerable support in the innovative method used here, which could determine the concentrations of a large number of trace elements (including heavy metals) in the black crusts examined, and thus could also be used as a reliable indicator of environmental pollution.

Background, aim, and scope This study developed an integrated approach to identify pollutant sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) of workers based on their blood contents. Materials and methods We first measured blood PCDD/F contents of sinter plant workers and residents living near the plant. By comparing those blood indicatory PCDD/Fs found for residents with those for sinter plant workers, exposure-related blood indicatory PCDD/Fs were identified for each selected worker. We then measured PCDD/F concentrations of four different sinter plant workplaces and three different ambient environments of the background. By comparing those airborne indicatory PCDD/Fs found for ambient environments with those for sinter plant workplaces, exposure-related airborne indicatory PCDD/Fs for each workplace were obtained. Finally, by matching exposure-related blood indicatory PCDD/Fs with exposure-related airborne indicatory PCDD/Fs, all suspected pollutant sources were identified for each selected worker. Results Poor Pearson correlations were found between workers' blood contents and their corresponding PCDD/F exposures. Significant differences were found in the top three blood indicatory PCDD/Fs among the selected workers. By matching exposure-related blood indicatory PCDD/Fs with exposure-related airborne indicatory PCDD/Fs, two to three suspected pollutant sources were identified for each selected worker. Discussion The poor Pearson correlation found between workers' airborne PCDD/Fs exposures and their blood contents was because workers' blood PCDD/Fs contents were contributed not only by workers' occupational exposures, but also by other exposure sources and exposure routes. The difference in blood indicatory PCDD/Fs among the selected workers were obviously due to the intrinsic differences in their time/activity patterns in the involved workplaces. While workers used a dust respirator to perform their jobs, gas phase exposure-related airborne indicatory PCDD/Fs played an important role on identifying suspected pollutant sources. But if a dust respirator was not used, the gas + particle phase exposure-related airborne indicatory PCDD/Fs would become the key factor for identifying suspected pollutant sources. Conclusions The developed integrated approach could identify all suspected pollutant sources effectively for selected workers based on their blood contents. The identified pollutant sources were theoretically plausible since they could be verified by examining workers' time/activity patterns, their status in using dust respirators, and the concentrations of PCDD/Fs found in the selected workplace atmospheres. Recommendations and perspectives The developed technique can be used to identify possible pollutant sources not only for workers but also for many other exposure groups associated with various emission sources and exposure routes in the future.

Background, aim, and scope Carbonyl compounds have been paid more and more attention because some carbonyl species have been proven to be carcinogenic or a risk for human health. Plant leaves are both an important emission source and an important sink of carbonyl compounds. But the research on carbonyl compounds from plant leaves is very scarce. In order to make an approach to the emission mechanism of plant leaves, a new method was established to extract carbonyl compounds from fresh plant leaves. Materials, methods, and results The procedure combining derivatization with ultrasonication was developed for the fast extraction of carbonyl compounds from tree leaves. Fresh leaves (< 0.01 g) were minced and ultrasonicated in acidic 2,4-dinitrophenylhydrazine (DNPH)-acetonitrile solution for 30 min and then holding 30 min to allow aldehydes and ketones in leaves to react completely with DNPH. Conclusions The extraction process was performed under room temperature and only took 60 min. The advantages of this method were very little sample preparation, requiring short treatment time and usual equipment. Four greening trees, i.e., camphor tree (Cinnamomum camphora), sweet olive (Osmanthus fragrans), cedar (Cedrus deodara), and dawn redwood (Metasequoia glyptostroboides), were selected and extracted by this method. Seven carbonyl compounds, including formaldehyde, acetaldehyde, acetone, acrolein, p-tolualdehyde, m/o-tolualdehyde, and hexaldehyde were determined and quantified. The most common carbonyl species of the four tree leaves were formaldehyde, acrolein, and m/o-tolualdehyde. They accounted for 67.3% in cedar, 50.8% in sweet olive, 45.8% in dawn redwood, and 44.6% in camphor tree, respectively. Camphor tree had the highest leaf level of m/o-tolualdehyde with 15.0 ± 3.4 µg g⁻¹(fresh leaf weight), which indicated that camphor tree may be a bioindicator of the level of tolualdehyde or xylene in the atmosphere. By analyzing carbonyl compounds from different tree leaves, it is not only helpful for further studying the relationship between sink and emission of carbonyls from plants, but also helpful for exploring optimum plant population in urban greening.

Background, aim and scope In an international project named MONARPOP (Monitoring Network in the Alpine Region for Persistent and other Organic Pollutants), selected chemicals in different environmental media were analysed in the years 2004 and 2005. Seventeen pesticides were chosen and analysed in humus and mineral soil in the German Alps. The samples were taken at different altitudes. Materials and methods In such a rather complex environmental datasets, it is often necessary to compare different sets of criteria and their influence on rankings. In the similarity analysis which is part of the theory of the Hasse diagram technique, we intend to calculate the similarity of different rankings. Furthermore, we perform a so-called dominance-dominance/dominance-separability method, followed by a sensitivity analysis, both subroutines in the newly developed PyHasse programme in order to find out if the concentration of the chemicals can be related to the altitudes at which the samples were taken. Results and discussion It can be demonstrated that the altitude has a considerable influence on the concentration of some organic chemicals in humus: The concentrations of some chemicals increase with the altitude. This increase shows certain irregularities for which several explication attempts including possible effects of atmospheric stratification phenomena in valleys have been made. Conclusion These results should be complemented in further studies with MONARPOP monitoring data from other Alpine countries, e.g. Austria, Switzerland, Italy and Slovenia.

Background, aim, and scope The aim of the study was to identify the impact of polychlorinated dibenzo-p-dioxin and furan (PCDD/F) emission sources on ambient air concentrations in the Malopolska Region, southern Poland. Three sites were selected: the city center of Krakow (Aleje), an industrial area (Nova Huta), and a rural site (Zakopane). In order to investigate the annual variations of PCDD/F sources, summer and winter time samples were taken. Materials and methods Ambient air particulate matter (PM10) was collected using an Anderson High-Volume sampler during June and December 2002 in the three mentioned sites. Analysis of PCDD/Fs was based on isotope dilution using high-resolution gas chromatography-high-resolution mass spectrometry for quantification. Results and discussion Total concentrations of 2,3,7,8-PCDD/Fs in air particulate phase from Malopolska region ranged from 0.6 to 37 pg m⁻³ (0.04-3.2 pg WHO₉₈-TEQ per cubic meter, 0.037-2.9 pg I-TEQ per cubic meter). Higher PCDD/F concentrations were measured at all three sites during winter. A linear correlation among PCDD/F concentrations, benzo(a)pyrene (B(a)P) and PM10 concentrations, was found in Aleje and Zakopane, which suggested that all compounds were originating from the same source, solid fuel domestic heating. Instead, PCDD/F levels in Nova Huta did not correlate with the seasonality of B(a)P or PM10 levels and 2,3,7,8-PCDD/F congener patterns for this site were significantly different from the other sites. Conclusions Domestic solid fuel combustion is likely the main PCDD/F source in winter in this part of Poland for urban and rural sites. PCDD/F fingerprints in the industrial site remained almost identical during summer and winter, confirming the yearly prevalence of the emissions from the nearby metal industry. Recommendations and perspectives PCDD/F concentrations found in Malopolska Region are in the upper range of ambient air concentrations of PCDD/Fs reported worldwide. However, further research is needed in order to study the impact of the deposition of these PCDD/F emissions on the region. A more extended study is being conducted in the area to analyze soil samples, such as sink of atmospheric deposition, and spruce needles, as indicator of PCDD/F availability.

Introduction Photochemical ozone pollution of the lower troposphere (LT) is a very complex process involving meteorological, topographic emissions and chemical parameters. Ozone is considered the most important air pollutant in rural, suburban and industrial areas of many sites in the world since it strongly affects human health, vegetation and forest ecosystems, and its increase during the last decades has been significant. In addition, ozone is a greenhouse gas that contributes to climate change. For these reasons, it is necessary to carry out investigations that determine the behaviour of ozone at different locations. The aim of this work is to understand the levels and temporal variations of surface ozone in an industrial-urban region of the Southwest Iberian Peninsula. Materials and methods The study is based on ozone hourly data recorded during a 6-year period, 2000 to 2005 at four stations and meteorological data from a coastal station. The stations used were El Arenosillo and Cartaya—both coastal stations, Huelva—an urban site and Valverde—an inland station 50 km away from the coastline. The general characteristics of the ozone series, seasonal and daily ozone cycles as well as number of exceedances of the threshold established in the European Ozone Directive have been calculated and analysed. Results Analysis of the meteorological data shows that winter-autumn seasons are governed by the movement of synoptic weather systems; however, in the spring-summer seasons, both synoptic and mesoescale conditions exist. Average hourly ozone concentrations range from 78.5 ± 0.1 μg m⁻³ at Valverde to 57.8 ± 0.2 μg m⁻³ at Huelva. Ozone concentrations present a seasonal variability with higher values in summer months, while in wintertime, lower values are recorded. A seasonal daily evolution has also been found with minimum levels around 08:00 UTC, which occurs approximately 1-1.5 h after sunrise, whereas the maximum is reached at about 16:00 UTC. Furthermore, during summer, the maximum value at El Arenosillo and Valverde stations remains very uniformed until 20:00 UTC. These levels could be due to the photochemical production in situ and also to the horizontal and vertical ozone transport at El Arenosillo from the reservoir layers in the sea and in the case of Valverde, the horizontal transport, thanks to the marine breeze. Finally, the data have been evaluated relative to the thresholds defined in the European Ozone Directive. The threshold to protect human health has been exceeded during the spring and summer months mainly at El Arenosillo and Valverde. The vegetation threshold has also been frequently exceeded, ranging from 131 days at Cartaya up to 266 days at Valverde. Discussion The results in the seasonal and daily variations demonstrate that El Arenosillo and Valverde stations show higher ozone concentrations than Cartaya and Huelva during the spring and summer months. Under meteorological conditions characterized by land-sea breeze circulation, the daytime sea breeze transports the emissions from urban and industrial sources in the SW further inland. Under this condition, the area located downwind to the NE is affected very easily by high ozone concentrations, which is the case for the Valverde station. Nevertheless, according to this circulation model, the El Arenosillo station located at the coast SE from these sources is not directly affected by their emissions. The ozone concentrations observed at El Arenosillo can be explained by the ozone residual layer over the sea, similar to other coastal sites in the Mediterranean basin. Conclusions The temporal variations of the ozone concentrations have been studied at four measurement sites in the southwest of the Iberian Peninsula. The results obtained point out that industrial and urban emissions combined with specific meteorological conditions in spring and summer cause high ozone levels which exceed the recommended threshold limits and could affect the vegetation and human health in this area. Recommendations and perspectives This work is the first investigation related to surface ozone in this region; therefore, the results obtained may be a useful tool to air quality managers and policy-makers to apply possible air control strategies towards a reduction of ozone exceedances and the impact on human health and vegetation. Due to the levels, variability and underlying boundary layer dynamics, it is necessary to extend this research in this geographical area with the purpose of improving the understanding of photochemical air pollution in the Western Mediterranean Basin and in the south of the Iberian Peninsula.

Background, aim, and scope Lead, a major contaminant, is highly used in paint manufacturing due to its anticorrosive properties. Recent reports indicated high lead content among Indian paints used for commercial purposes. Painters are continuously exposed to these lead containing paints during painting of both commercial as well as residential buildings. Lead is well-known for its genotoxicty in occupational workers; however, in Indian painters the genotoxic effects of lead have not been reported to date. Therefore we aimed to study the genotoxic end points in painters due to their long-term exposure to these high lead-containing Indian paints. Materials and methods Study group selection was made after a questionnaire administration, which included questions about lifestyle and medical history to exclude exposure to the other potential sources of genotoxics. Blood and buccal cell samples were obtained from 30 male painters and from a similar number of age-matched controls of same location with no occupational exposure to lead. Blood lead levels (Pb-B) were measured in painters and controls. Micronucleus (MN) frequencies and nuclear changes, i.e., karyorrhexis, karyolysis, broken egg, and binucleated, were investigated in buccal epithelial cells. Results Painters had significantly (P < 0.01) greater lead levels in blood than the control group. MN frequencies and nuclear changes in buccal epithelial cells were also significantly (P < 0.01) elevated in painters as compared with control subjects. Regression analysis also revealed significant (P < 0.01) association of Pb-B with all the genotoxic endpoints in painters. Cytogenetic damage was significantly associated with Pb-B as no other co-founding factors (smoking, alcohols) showed significant difference between both groups. Discussion Lead is widely used in paints which may serve as potential source of exposure among painters due to their long-term engagement with paints. Our results clearly demonstrated genotoxicity among the exposed population as evident from increase micronucleus frequencies, frequent nuclear changes, and apoptosis. Many studies had previously related nuclear change events in buccal epithelial cells with the progression of different carcinomas. Furthermore in-depth investigations with larger sample size are needed to provide evidence to this effect. Conclusions Here, we report cytogenetic toxicity to the exposed population by the high lead containing paints from India for the first time. Frequent, high and unregulated use of lead in paints may cause genetic mutation and may accelerate cytogenetic damage which may further lead to different carcinomas in painters. These findings need to be considered and necessary steps should be taken to protect the occupational workers engaged with these high lead-containing paints. Recommendations The use of lead in paints is completely unregulated in India and routine surveillance of paints for lead content is still lacking. These paints are readily available in markets and are also used in other products (jewelry, miniblinds) which could be exported to other countries including United States and Europe. Serious consideration should be given to the inclusion of regulations and bans on the use of lead in paints. Moreover, attention should also be paid towards the use of various protective measures (face-masks, hand gloves, and separate clothes) by the workers as safe work practices during working periods.

Background, aim, and scope Anti-tumour agents and their metabolites are largely excreted into effluent, along with other pharmaceuticals. In the past, investigations have focused on the input and analysis of pharmaceuticals in surface and ground water. The two oxazaphosphorine compounds, cyclophosphamide and ifosfamide are important cytostatic drugs used in the chemotherapy of cancer and in the treatment of autoimmune diseases. Their mechanism of action, involving metabolic activation and unspecific alkylation of nucleophilic compounds, accounts for genotoxic and carcinogenic effects described in the literature and is reason for environmental concern. The anti-tumour agents cyclophosphamide (CP) and ifosfamide (IF) were not biodegraded in biodegradation tests. They were not eliminated in municipal sewage treatment plants. Degradation by photochemically formed HO radicals may be of some relevance only in shallow, clear, and nitrate-rich water bodies but could be further exploited for elimination of these compounds by advanced oxidation processes, i.e. in a treatment of hospital waste water. Therefore, CP and IF are assumed to persist in the aquatic environment and to enter drinking water via surface water. The risk to humans from input of CP and IF into surface water is not known. Materials and methods The local and regional, i.e. nationwide predicted environmental concentration (PEClocal, PECregional) of CP and IF was calculated for German surface water. Both compounds were measured in hospital effluents, and in the influent and effluent of a municipal treatment plant. Additionally, published concentrations in the effluent of sewage treatment plants and surface water were used for risk assessment. Excretion rates were taken into account. For a worst-case scenario, maximum possible ingestion of CP or IF by drinking 2 L a day of unprocessed surface water over a life span of 70 years was calculated for adults. Elimination in drinking water processing was neglected, as no data is available. This intake was compared with intake during anti-cancer treatment. Results and discussion Intake of CP and IF for anti-cancer treatment is typically 10 g within a few months. Under such conditions, a relative risk of 1.5 for the carcinogenic compounds CP and IF is reported in the literature. In the worst case, the maximum possible intake by drinking water is less than 10⁻³ (IF) and 10⁻⁵ (CP) of this amount, based on highest measured local concentrations. On a nationwide average, the factor is approx. 10⁻⁶ or less. Conclusions The additional intake of CP and IF due to their emission into surface water and its use without further treatment as drinking water is low compared to intake within a therapy. This approach has shortcomings. It illustrates the current lack of methodology and knowledge for the specific risk assessment of carcinogenic pharmaceuticals in the aquatic environment. IF and CP are directly reacting with the DNA. Therefore, with respect to health effects a safe threshold concentration for these compounds cannot be given. The resulting risk is higher for newborns and children than for adults. Due to the lack of data the risk for newborns and children cannot be assessed fully. The data presented here show that according to present knowledge the additional risk of cancer cannot be fully excluded, especially with respect to children. Due to the shortage of data for effects of CP and IF in low doses during a whole lifespan, possible effects were assessed using data of high doses of CP and IF within short-term ingestion, i.e. therapy. This remains an unresolved issue. Anyway, the risk assessment performed here could give a rough measure of the risks on the one hand and the methodological shortcomings on the other hand which are connected to the assessment of the input of genotoxic and carcinogenic pharmaceuticals such as CP and IF into the aquatic environment. Therefore, we recommend to take measures to reduce the input of CP and IF and other carcinogenic pharmaceuticals. We hope that our manuscript further stimulates the discussion about the human risk assessment for carcinogenic pharmaceuticals in the aquatic environment. Recommendations and perspectives CP and IF are carcinogens. With respect to newborn and children, reduction of the emission of CP and IF into effluent and surface water is recommended at least as a precautionary measure. The collection of unused and outdated drugs is a suitable measure. Collection of patients' excreta as a measure of input reduction is not recommended. Data suitable for the assessment of the risk for newborn and children should be collected in order to perform a risk assessment for these groups. This can stimulate discussion and give new insights into risk assessment for pharmaceuticals in the environment. Our study showed that in the long term, effective risk management for the reduction of the input of CP and IF are recommendable.

Purpose In this study, seasonal variations in the concentration profile of four analgesics and one lipid regulator were monitored on their way from a wastewater treatment plant (WWTP) effluent, along a river, and into a lake. Methods From December 2007 to December 2008, water samples were collected monthly (n = 12) from an upstream point, the effluent, four downstream points of the WWTP, and at the point where the river merges with the lake, and the concentrations of ibuprofen, naproxen, bezafibrate, diclofenac, and ketoprofen were determined. The analytical methodology involved solid-phase extraction of the target compounds from water samples followed by liquid chromatography coupled with tandem mass spectrometry for compound separation and detection. Results The studied pharmaceuticals were found in the effluent at concentrations ranging from 31 to 1,852 ng l⁻¹ depending on the season. In the river and lake, the concentrations were much lower (6-400 ng l⁻¹) mainly due to dilution but also to a season-dependent contribution from natural transformation processes. The mean mass flow of all analgesics was highest during winter while the highest mean mass flow of the lipid regulator bezafibrate was observed in spring. Conclusions The WWTP is the main source of the target compounds in the aquatic environment. The observed winter accumulation signifies the importance of natural transformation processes, which can only be estimated based on mass flow data, on the fate of pharmaceuticals in the environment.

Background, aim, and scope In the Water Framework Directive 2000/60/EC, environmental objectives for the proper quality of inland, surface, transitional, coastal, and ground waters have been set. Member states are required to identify chemical pollutants of significance in the water bodies, to establish emission control measures, and to achieve quality standards. A specific category of pollutants are the compounds that may possess endocrine-related functions known as endocrine disrupting compounds (EDCs). This means that member states have the obligation to take action in order to prevent human exposure to these compounds via aquatic environment. The objective of this research was to study the occurrence and distribution of phenolic and steroid EDCs in inland waters and wastewaters discharged in the area of Thermaikos Gulf, Thessaloniki, Northern Greece. Materials and methods Samples were collected from three rivers, four streams, and four municipal and industrial wastewaters from the area of Thessaloniki, Northern Greece, during the period 2005-2006. The samples were analyzed for 14 EDCs (nonylphenol, octylphenol, their mono- and di-ethoxylate oligomers, bisphenol A, estrone, 17α-estradiol, 17β-estradiol, estriol, mestranol, and 17α-ethynylestradiol). The compounds were recovered by solid phase extraction and ultrasonic extraction from the dissolved phase and particulate phase, respectively, and determined by employing gas chromatography-mass spectrometry. Results Results revealed the presence of phenolic EDCs (NP, NP1EO, NP2EO, tOP, OP1EO, OP2EO, and BPA) in all water and wastewater samples. Steroid EDCs were not found at detectable concentrations. The relationships between field partition coefficients of EDCs and concentration of total suspended solids, dissolved, and particulate organic carbon were investigated. Discussion Rivers exhibited concentrations of EDCs similar to minimally impacted surface waters worldwide. The concentrations of NP and OP occasionally exceeded the environmental quality criteria proposed for inland waters. The concentrations of EDCs in streams exhibited wide variations due to low flow rate in these systems and the impact of wastewaters from various pollution sources. Wastewater from tannery activities showed extremely high concentrations of NP, whereas relatively high concentrations of EDCs were determined in effluents from the industrial wastewater treatment plant. Field partition coefficients of EDCs are negatively correlated with concentrations of total suspended solids and dissolved organic carbon and positively correlated with particulate organic carbon. Conclusions The examined rivers (Aliakmon, Axios, and Loudias) exhibited concentrations of EDCs similar to minimally impacted surface waters worldwide. However, special attention should be paid to these systems since the concentrations for NP and OP occasionally were above the proposed quality standards, revealing the impact of urban, industrial, and agricultural activities. High concentrations of EDCs were determined in streams, urban, and industrial wastewater posing significant risk to the aquatic environment they discharged. Recommendations and perspectives The occurrence of EDCs in inland waters and wastewaters discharged to Thermaikos Gulf results in an increased risk to the marine environment. Thus, these systems should be regularly monitored, especially for NP, OP, and BPA that are considered as priority hazardous compounds in the Water Framework Directive.