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On behalf of Aluminiumindustriens Miljøsekretariat (AMS) and Alcoa Lista, NILU – Norwegian institute for air research has conducted a sampling campaign in the surroundings of the Alcoa Lista aluminium smelter in order to update the knowledge on PAH-concentrations around the smelter today. Samples were taken in the period January – December 2020 and analysed for particle bound PAHs. As a consequence of reduced emissions compared to earlier measurements, the ambient concentrations of benzo(a)pyrene (BaP) were reduced. BaP had an annual average concentration below the target value at both sampling sites. At Huseby, the lower assessment threshold was exceeded. PAH-levels in the area were similar to those observed in Norwegian cities. NILU – Norsk institutt for luftforskning har, på oppdrag fra Aluminiumindustriens Miljøsekretariat (AMS) og Alcoa Lista, tatt PAH-prøver i omgivelsene til Alcoa Lista aluminiums-smelteverk for å oppdatere kunnskapen om PAH-konsentrasjoner rundt smelteverket i dag. Prøvene ble tatt i perioden januar – desember 2020 og analysert for partikkelbundne PAHer. Som en konsekvens av reduserte utslipp sammenlignet med tidligere målinger, er konsentrasjonen av benzo(a)pyren (BaP) redusert. Årsmiddelet av BaP-konsentrasjonen i 2020 var under målsettingsverdien på begge prøvetakingsstedene. På Huseby ble den nedre vurderingsterskelen overskredet. PAH-konsentrasjonen i området på samme nivå som i norske byer.

Prosjektleder Anders Ruus Tizir Titanium & Iron AS hadde et uhellsutslipp av 217 kg PAH-forbindelser i løpet av 28 timer i juni 2020. Kortsiktige og langsiktige effekter av utslippet ble vurdert. Tidligere modellering av fortynning og spredning av bedriftens regulerte utslippspunkt ble benyttet. Beregnede konsentrasjoner av PAH-forbindelser i vannsøyle ved diffusor og ca. 1 km fra diffusor (nordvestlig retning) viste at grenseverdier for flere PAH-forbindelser ble oversteget i løpet av de 28 timene uhellsutslippet vedvarte. Beregnede kortvarige konsentrasjoner kan gi akutte toksiske effekter på organismer inntil 1 km fra diffusor. Blåskjell innsamlet ca. to måneder etter uhellsutslippet hadde tilsvarende konsentrasjoner av PAH som i blåskjell samlet inn i 2019. Konsentrasjonene var godt under grenseverdier gitt i vannforskriften. En konservativ og teoretisk beregning av tilførsler av PAH til sedimenter utenfor Tizir Titanium & Iron AS, indikerer at tilførslene av PAH er beskjedne i forhold til de eksiterende konsentrasjonene i sedimentene. NIVA kan ikke se at det noen tiltak som kan iverksettes for å motvirke konsekvenser av utslippet. En blåskjellstasjon ved Apold bør følges opp videre.

BACKGROUND Particulate matter 2.5 (PM2.5) in air pollution is regarded as a risk factor for cardiovascular disease (CVDs). Recently, it has become well accepted that polycyclic aromatic hydrocarbons (PAHs) in PM2.5 impacts human CVDs. However, few studies have shown miRNAs affected by PAHs play a critical role in transcriptional regulation related to cardiovascular development and disease. MATERIAL AND METHODS Human umbilical cord vein cells (HUVECs) incubated prior to treatment with PAHs at various concentrations (0, 100, 200, 300, 400, and 500 µg/ml) of PAHs particle solutions were added to the culture medium for 24 h. We performed isolation and sequencing of small RNAs and analysis of small RNA sequences and differential expression. The M3RNA database was used to predict miRNA-miRNA interactions. Tools from the DAVID database were used to perform the GO functional analysis of predicted miRNA target genes. A First-Strand cDNA Synthesis Kit was used to synthesis cDNA. RESULTS miRNA155 was revealed as a key regulator in PAHs treatment. The putative targets of upregulated miRNA in PAHs treatment indicated that the downregulated genes were enriched in biological pathways such as Wnt signaling and ErbB signaling, which are crucial for the development of vasculature. CONCLUSIONS In general, our results suggest that PAHs taken by PM2.5 can decrease cardiovascular-related gene expression through upregulating miRNA, which may be a new target for therapy in the future.

Inventory of emission sources and biomonitoring with moss transplants are two different methods to evaluate air pollution. In this study, for the first time, both these approaches were simultaneously applied in five municipalities in Campania (southern Italy), deserving attention for health-oriented interventions as part of a National Interest Priority Site. The pollutants covered by the inventory were CO, NOx, particulate matter (PM10), volatile organic compounds (VOCs), and some heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb, Se, and Zn). The biomonitoring survey was based on the use of the devitalized moss Hypnum cupressiforme transplanted into bags, following a harmonized protocol. The exposure covered 40 agricultural and urban/residential sites, with half of them located in proximity to roads. The pollutants monitored were Al, As, Cd, Cr, Cu, Fe, Hg, Ni, Pb, Se, and Zn, as well as total polycyclic aromatic hydrocarbons (PAHs) only in five sites. Using the emission inventory approach, high emission loads were detected for all the major air pollutants and the following heavy metals: Cr, Cu, Ni, Pb and Zn, over the entire study area. Arsenic, Pb, and Zn were the elements most accumulated by moss. Total PAH postexposure contents were higher than the preexposure values (~20–50% of initial value). Moss uptakes did not differ substantially among municipalities or within exposure sites. In the five municipalities, a similar spatial pattern was evidenced for Pb by emission inventory and moss accumulation. Both approaches indicated the same most polluted municipality, suggesting their combined use as a valuable resource to reveal contaminants that are not routinely monitored.

OBJECTIVES: Workers' exposure to diesel exhaust in a bus depot, a truck repair workshop and an underground tunnel was determined by the measuring of elemental carbon (EC) and 15 carcinogenic polycyclic aromatic compounds (PACs) proposed by the US Department of Health and Human Services/National Toxicology Program (NTP). Based on these concentration data, the genotoxic PAC contribution to the diesel-exhaust particle (DEP) lung-cancer risk was calculated. METHOD: Respirable particulate matter was collected during the summer and winter of 2001 (except for in the underground situation) and analysed by coulometry for EC and by GC-MS methods for PACs. The use of potency equivalence factors (PEFs) allowed the studied PAC concentrations to be expressed as benzo[a]pyrene equivalents (B[a]P(eq)). We then calculated the lung-cancer risk due to PACs and DEPs by multiplying the B[a]P(eq) and EC concentrations by the corresponding unit risk factor. The ratio of these two risks values has been considered as an estimate of the genotoxic contribution to the DEP cancer risk. RESULTS: For the bus depot and truck repair workshop, exposure to EC and PACs has been shown to increase by three to six times and ten times, respectively, during winter compared to summer. This increase has been attributed mainly to a decrease in ventilation during the cold. With the PEF approach, the B[a]P(eq) concentration is five-times higher than if only benzo[ a]pyrene (B[a]P) is considered. Dibenzopyrenes contribute an important part to this increase. A simple calculation based on unit risk factors indicates that the studied PAC contribution to the total lung-cancer risk attributed to DEPs is in the range of 3-13%. CONCLUSIONS: The 15 NTP PACs represent a small but non-negligible part of lung-cancer risk with regard to diesel exposure. From this point of view, the dibenzopyrene family are important compounds to be considered.

Prosjektleder Atle Hindar Kristiansand kommune tok i 2016 initiativ til å få utarbeidet et forurensningsregnskap for deler av Kristiansandsfjorden. Det var et mål å skaffe mer kunnskap om alle relevante forurensningskilder og forurensningsbidraget fra disse til fjorden. I 2016 og 2017 ble det gjennomført prøvetaking for analyse av metaller og PAH i avrenningen fra Baneheia (ubebygd) og i overvannet i Kvadraturen (tre bygater). Resultater og beregninger inngår i forurensningsregnskapet. I rapporten presenteres først en prosedyre og deretter hvordan vi ved bruk av prosedyren har kommet fram til forurensningsregnskap for de geografisk avgrensede regnskapsområdene Østre havn, Vesterhavn og Fiskåbukta. Forurensningsregnskapene er utarbeidet for PAH og metallene kopper, nikkel, sink og bly. I Vesterhavn og Fiskåbukta er industriutslippene til vann av hhv Cu og Ni fra Glencore Nikkelverk og PAH fra Elkem Carbon dominerende kilder. I Østre havn er småbåthavnene dominerende kilde for Cu og Zn. Både sjøsedimentene og avrenningen fra land er viktige kilder for PAH, Ni og Pb i Østre havn og generelt for Zn og Pb. Odderøya RA har et tydelig bidrag til PAH og Zn i Vesterhavn. Miljødirektoratet

Ambient air polycyclic aromatic hydrocarbon (PAH) samples were collected at traffic, residential, coastal, and semiurban sites in Bursa, Turkey, between June 2008 and June 2009. For the traffic, residential, coastal, and semiurban sites, the average gas phase total PAH (a(12)PAH) concentrations were 113 +/- A 131, 142 +/- A 204, 53 +/- A 73, and 19 +/- A 34 ng/m(3), respectively, whereas the average particle phase total PAH concentrations were 28 +/- A 36, 56 +/- A 85, 24 +/- A 40, and 11 +/- A 23 ng/m(3), respectively. Phenanthrene and fluoranthene had the highest concentrations of all of the sampling sites in the gas phase. The PAH concentrations in the heating period were 5-7 times greater than the nonheating period concentrations. Principal component analysis (PCA) was used to investigate the relationship between the levels of PAHs determined in ambient samples and their possible sources. The PCA model shows that coal combustion and vehicle emissions affected PAH emissions. Moreover, the molecular diagnostic ratios indicated that coal-burning and traffic emissions were the dominant PAH sources. The multiple linear regression analysis indicated that the meteorological parameters also affected the ambient PAH concentrations. The sampling site characteristics, meteorological conditions, dispersion, and local sources all affected the concentration levels.

Removal of polycyclic aromatic hydrocarbons (PAHs) existed in automotive industry treatment sludge was examined by considering the effects of temperature, UV, titanium dioxide (TiO2) and diethyl amine (DEA) in different dosages (i.e., 5% and 20%) in this study. Application of TiO2 and DEA to the sludge samples in ambient environment was studied. Ten PAH (Sigma(10) PAH) compounds were targeted and their average value in the sludge was found to be 4480 +/- 1450 ng/g dry matter (DM). Total PAH content of the sludge was reduced by 25% in the ambient air environment. Meteorological conditions, atmospheric deposition, evaporation and sunlight irradiation played an effective role in the variations in PAH levels during the tests carried out in ambient air environment. Moreover, it was observed that when the ring numbers of PAHs increased, their removal rates also increased. Total PAH level did not change with the addition of 5% DEA and only 10% decreased with 5% TiO2 addition. PAH removal ratios were 8% and 32% when DEA (20%) and TiO2 (20%) were added, respectively. It was concluded that DEA was a weak photo-sensitizer yet TiO2 was effective only at 20% dosage.

Harbours are important hubs for economic growth in both tourism and commercial activities. They are also an environmental burden being a source of atmospheric pollution often localized near cities and industrial complexes. The aim of this study is to quantify the relative contribution of maritime traffic and harbour activities to atmospheric pollutant concentration in the Venice lagoon. The impact of ship traffic was quantified on various pollutants that are not directly included in the current European legislation for shipping emission reduction: (i) gaseous and particulate PAHs; (ii) metals in PM10; and (iii) PM10 and PM2.5. All contributions were correlated with the tonnage of ships during the sampling periods and results were used to evaluate the impact of the European Directive 2005/33/EC on air quality in Venice comparing measurements taken before and after the application of the Directive (year 2010). The outcomes suggest that legislation on ship traffic, which focused on the issue of the emissions of sulphur oxides, could be an efficient method also to reduce the impact of shipping on primary particulate matter concentration; on the other hand, we did not observe a significant reduction in the contribution of ship traffic and harbour activities to particulate PAHs and metals. Graphical abstract Impact of maritime traffic on polycyclic aromatic hydrocarbons, metals and particulate matter and evaluation of the effect of an European Directive on air quality in Venice.

Fine particulate matter (PM1 and PM2.5) was collected in Milan over the summer (August-September) and winter (January-March) seasons of 2007/2008. Particles were analyzed for their chemical composition (inorganic ions, elements and PAHs) and the effects produced on the human lung carcinoma epithelial cell line A549. In vitro tests were performed to assess cell viability with MTT assay, cytokine release (IL-6 and IL-8) with ELISA, and DNA damage with COMET assay. Results were investigated by bivariate analysis and multivariate data analysis (Principal Component Analysis, PCA) to investigate the relationship between PM chemical composition and the biological effects produced by cell exposure to 12 microg cm(-2). The different seasonal chemical composition of PM showed to influence some biological properties. Summer PM samples had a high mass contribution of SO(4)(=) (13+/-2%) and were enriched in some elements, like Al, As, Cr, Cu, and Zn, compared to winter PM samples. Cell viability reduction was two times higher for summer PM samples in comparison with winter ones (27+/-5% and 14+/-5%, respectively), and the highest correlation coefficients between cell viability reduction and single chemical components were with As (R(2)=0.57) and SO(4)(=) (R(2)=0.47). PM1 affected cell viability reduction and induced IL-8 release, and these events were interrelated (R(2)=0.95), and apparently connected with the same chemical compounds. PM2.5 fraction, which was enriched in Ca(++) and Mg(++) (from soil dust), and Al, Fe, Zn, Ba Mn, produced cell viability reduction and DNA damage (R(2)=0.73).

Effects of space heating on atmospheric concentrations and gas-particle partitioning of PAHs were investigated in a suburban site of Bursa, Turkey. The average concentrations of Sigma(15)-PAHs in heating season samples were approximately 10 times higher than those of non-heating season samples. The plot of log K-p versus log P-L(0) for all the data set gave significantly different slopes. The slope for the heating season (-0.75) samples was steeper than the one for the non-heating season (-0.64) samples. It was also observed that partitioning of PAHs for the non-heating season samples showed different characteristics depending on air parcel trajectories. Generally steeper slopes were obtained for the air parcels traveled across the Black sea and arrived to the sampling site from northern sector. On the other hand, the variations in slopes according to air mass origin were insignificant for the heating season samples. Local contributions from space heating are the reason for this observation. (c) 2007 Elsevier Ltd. All rights reserved.

Disruption of cell proliferation control by polycyclic aromatic hydrocarbons (PAHs) may contribute to their carcinogenicity. We investigated role of the aryl hydrocarbon receptor (AhR) in disruption of contact inhibition in rat liver epithelial WB-F344 'stem-like' cells, induced by the weakly mutagenic benz[a]anthracene (BaA), benzo[b]fluoranthene (BbF) and by the strongly mutagenic benzo[a]pyrene (BaP). There were significant differences between the effects of BaA and BbF, and those of the strongly genotoxic BaP. Both BaA and BbF increased percentage of cells entering S-phase and cell numbers, associated with an increased expression of Cyclin A and Cyclin A/cdk2 complex activity. Their effects were significantly reduced in cells expressing a dominant-negative AhR mutant (dnAhR). Roscovitine, a chemical inhibitor of cdk2, abolished the induction of cell proliferation by BbF. However, neither BaA nor BbF modulated expression of the principal cdk inhibitor involved in maintenance of contact inhibition, p27(Kip1), or pRb phosphorylation. The strongly mutagenic BaP induced apoptosis, a decrease in total cell numbers and significantly higher percentage of cells entering S-phase than either BaA or BbF. Given that BaP induced high levels of Cyclin A/cdk2 activity, downregulation of p27(Kip1) and hyperphosphorylation of pRb, the accumulation of cells in S-phase was probably due to cell proliferation, although S-phase arrest due to blocked replication forks can not be excluded. Both types of effects of BaP were significantly attenuated in dnAhR cells. Transfection of WB-F344 cells with siRNA targeted against AhR decreased induction of Cyclin A induced by BbF or BaP, further supporting the role of AhR in proliferative effects of PAHs. This suggest that activation of AhR plays a significant role both in disruption of contact inhibition by weakly mutagenic PAHs and in genotoxic effects of BaP possibly leading to enhanced cell proliferation. Thus, PAHs may increase proliferative rate and the likelihood of fixation of mutations. This work was partly supported by ECNIS, European Union 6th Framework Program, Priority 5: “Food Quality and Safety” (Contract No. 513943).

There has been limited study of the removal of polycyclic aromatic hydrocarbons (PAHs) from inorganic clay minerals. Determining the amount of PAH removal is important in predicting their environmental fate. This study was carried out to the degradation and evaporation of PAHs from bentonite, which is an inorganic clay mineral. UV apparatus was designed specifically for the experiments. The impacts of temperature, UV, titanium dioxide (TiO2), and diethylamine (DEA) on PAH removal were determined. After 24 h, 75 and 44 % of Sigma(12) PAH in the bentonite were removed with and without UV rays, respectively. DEA was more effective as a photocatalyst than TiO2 during UV application. The Sigma(12) PAH removal ratio reached 88 % with the addition of DEA to the bentonite. It was concluded that PAHs were photodegraded at high ratios when the bentonite samples were exposed to UV radiation in the presence of a photocatalyst. At the end of all the PAH removal applications, higher evaporation ratios were obtained for 3-ring compounds than for heavier ones. More than 60 % of the amount of Sigma(12) PAH evaporated consisted of 3-ring compounds.

Near-ground air (26 substances) and surface seawater (55 substances) concentrations of persistent toxic substances (PTS) were determined in July 2012 in a coordinated and coherent way around the Aegean Sea based on passive air (10 sites in 5 areas) and water (4 sites in 2 areas) sampling. The direction of air–sea exchange was determined for 18 PTS. Identical samplers were deployed at all sites and were analysed at one laboratory. hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs) as well as dichlorodiphenyltrichloroethane (DDT) and its degradation products are evenly distributed in the air of the whole region. Air concentrations of p,p′-dichlorodiphenyldichloroethylene (p,p′-DDE) and o,p′-DDT and seawater concentrations of p,p′-DDE and p,p′-DDD were elevated in Thermaikos Gulf, northwestern Aegean Sea. The polychlorinated biphenyl (PCB) congener pattern in air is identical throughout the region, while polybrominated diphenylether (PBDE)patterns are obviously dissimilar between Greece and Turkey. Various pollutants, polycyclic aromatic hydrocarbons (PAHs), PCBs, DDE, and penta- and hexachlorobenzene are found close to phase equilibrium or net-volatilisational (upward flux), similarly at a remote site (on Crete) and in the more polluted Thermaikos Gulf. The results suggest that effective passive air sampling volumes may not be representative across sites when PAHs significantly partitioning to the particulate phase are included., Granting Agency of the Czech Republic (312334); Czech Ministry of Education (LO1214--LM2011028); European Social Fund (CZ.1.07/2.3.00/30.0037); European Commission FP7 (262254 ACTRIS)

Within the framework of a Weight of Evidence (WoE) approach, a set of four toxicity bioassays involving the amphipod Corophium volutator (10 d lethality test on whole sediment), the sea urchin Paracentrotus lividus (fertilization and embryo toxicity tests on elutriate) and the pacific oyster Crassostrea gigas (embryo toxicity test on elutriate) was applied to sediments from 10 sampling sites of the Venice Lagoon (Italy). Sediments were collected during three campaigns carried out in May 2004 (spring campaign), October 2004 (autumn campaign) and February 2005 (winter campaign). Toxicity tests were performed on all sediment samples. Sediment grain-size and chemistry were measured during spring and autumn campaigns. This research investigated (i) the ability of toxicity tests in discriminating among sites with different contamination level, (ii) the occurrence of a gradient of effect among sampling sites, (iii) the possible correlation among toxicity tests, sediment chemistry, grain size and organic carbon, and (iv) the possible occurrence of toxicity seasonal variability. Sediment contamination levels were from low to moderate. No acute toxicity toward amphipods was observed, while sea urchin fertilization was affected only in few sites in just a single campaign. Short-term effects on larval development of sea urchin and oyster evidenced a clear spatial trend among sites, with increasing effects along the axis connecting the sea-inlets with the industrial area. The set of bioassays allowed the identification of a spatial gradient of effect, with decreasing toxicity from the industrial area toward the sea-inlets. Multivariate data analysis showed that the malformations of oyster embryos were significantly correlated to the industrial contamination (metals, polynuclear aromatic hydrocarbons, hexachlorobenzene and polychlorinated biphenyls), while sea urchin development to sediment concentrations of As, Cr and organic carbon. Both embryo toxicity tests were significantly affected by high ammonia concentrations found in the elutriates extracted from some mudflat and industrial sediments. No significant temporal variation of the toxicity was observed within the experimental period. Amendments to the set of bioassays, with inclusion of chronic tests, can certainly provide more reliability and consistency to the characterization of the (possible) toxic effects.

Organic films and leaves provide a medium into which organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs), can accumulate, resulting in a useful passive air sampler. In the present work, the temporal variability (weekly) in PAH concentrations and the fingerprint of films developed on window surfaces were investigated. Moreover, films and leaves of two tree species (Acer pseudoplatanus and Cornus mas) collected at the same time were used to derive PAH air concentrations and investigate their short-term variability. In general, the most abundant chemicals found in films were phenanthrene and pyrene (22%), followed by perylene (21%) and fluoranthene (16%), but the fingerprint (in contrast to leaves and air) changed over time. Leaf derived air concentrations were within a factor of 2 to 9 from measured values, while air concentrations back-calculated from films were within a factor of 2 to 53. This happened because predicted air concentrations using films and vegetation samplers (especially for low KOA chemicals) generally reflect only the last few hours (due to the fast equilibrium) of the weekly integrated samples obtained employing the high-volume sampler. This means that films and leaves can be usefully employed for predicting the short-term variability of low KOA organic contaminant air concentrations.

The Nador Lagoon holds a major interest in present-day Moroccan socioeconomic development. This environment is exposed to a number of potential polluting sources, such as mine tailings, urban and industrial dumping, and untreated wastewater inputs from surrounding cities. The aim of this study was to assess concentrations and trends of persistent contaminants such as PCBs and PAHs and to identify their origin. The non-Aroclor PCB-11 was determined for the first time in the lagoon sediments. Chronology and source assessment helped identifying the timing and nature of inputs and post-depositional processes controlling the two classes of contaminants: PAHs present a typical mixed petrogenic signature, with the exception of sediments deposited in the period 1930-1960 near the city of Nador, when pyrogenic inputs prevailed; PCBs show signs of microbial anaerobic degradation from 1950 to 1990, probably linked to changing hydrodynamic conditions in the South-Western part of the lagoon where agricultural inputs are dominant. The presence of PCB-11 is linked to specific productions and might be affected by degradation processes. Presently, different land uses (e.g., urban and agricultural areas) appear to be the key factors in controlling the level and composition of PAHs and PCBs in lagoon sediments. Total PAH and PCB levels are low (from 21.6 to 108ngg-1 and from 2.50 to 20.7ngg-1, respectively) but recent increasing values and the potential threat to humans and biota require continuous and constant monitoring.

OBJETIVO: Desenvolver estratégia para o monitoramento passivo das águas do estuário de Santos quanto à presença de atividade genotóxica e de hidrocarbonetos policíclicos aromáticos. MÉTODOS: Estudo realizado no estuário de Santos, Estado de São Paulo, em 2002. Foram selecionados e avaliados dois pontos de amostragem com diferentes graus de contaminação em duas campanhas de amostragem, utilizando a técnica de blue rayon in situ, análises químicas e o ensaio de Salmonella/microssoma com as linhagens bacterianas sensíveis a diferentes classes de compostos. Os extratos foram submetidos ao teste de Salmonella/microssoma em microssuspensão com as linhagens TA98, TA100, YG1041 e YG1042 na presença e ausência de ativação metabólica, e a análises químicas. RESULTADOS: O ponto 1, que apresentou sedimento com altas concentrações de hidrocarbonetos policíclicos aromáticos, mostrou maior freqüência de resultados positivos para o ensaio Samonella/microssoma e maiores concentrações de hidrocarbonetos policíclicos aromáticos em ambas as campanhas em comparação com o ponto 2, menos contaminado. A linhagem que se mostrou mais sensível foi a YG1041, que permitiu comparações entre locais com diferentes graus de contaminação. CONCLUSÕES: A combinação da técnica de blue rayon in situ com o ensaio Salmonella/microsoma com a linhagem YG1041 e as análises químicas se mostraram eficientes. Foi possível recuperar os compostos genotóxicos, e os hidrocarbonetos policíclicos aromáticos analisados, parecendo ser uma estratégia adequada para o monitoramento da qualidade das águas do estuário de Santos. OBJECTIVE: To develop a strategy for water quality monitoring for the presence of genotoxins and polycyclic aromatic hydrocarbons. METHODS: A study was carried out in Santos estuary, Southern Brazil, in 2002. Two sampling sites with different concentration levels were selected and evaluated in different samplings using blue rayon hanging technique, chemical analyses, and Salmonella/microsome assay with bacterial strains sensitive to different compounds. The extracts were tested using the Salmonella/microsome assay in microsuspension with the strains TA98, TA100, YG1041, and YG1042 in the absence and presence of metabolic activation and through chemical analyses. RESULTS: Site 1, which had high concentrations of polycyclic aromatic hydrocarbons in its sediment, showed more often positive results in the Salmonella/microsome assay as well as higher polycyclic aromatic hydrocarbons concentrations in both samplings compared to site 2, which was less contaminated. YG1041 strain showed to be the most sensitive allowing for comparisons between the sites with different levels of contamination. CONCLUSIONS: The combination of the blue rayon hanging technique with the Salmonella/microsome assay using YG1041 strain and chemical analyses were effective in recovering genotoxins as well as polycyclic aromatic hydrocarbons tested in this study. Therefore this strategy seems to be adequate for water quality monitoring in Santos estuary.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous air pollutants generated by combustion sources that include diesel- and gasoline-powered motor vehicles, coal-fired power plants, residential heating, cooking, and tobacco smoking (Bostrom et al. 2002). An estimated > 80% of airborne PAHs results from the combustion of fossil fuels and biomass (Bostrom et al. 2002). There is growing concern about the adverse effects of air pollution from fossil fuel combustion on public health (Bostrom et al. 2002; Brunekreef and Holgate 2002) and the global climate (National Academy of Sciences 2001). PAHs are human mutagens and carcinogens (Bostrom et al. 2002) and are potentially significant reproductive and developmental toxicants (Dejmek et al. 2000; Perera et al. 2003). For example, prenatal exposure of rats to 25–100 μg/m3 of the representative PAH, benzo[a]pyrene (BaP), through maternal inhalation significantly decreased the fetal survival rate and birth weight in a dose-dependent manner (Archibong et al. 2002). In humans, associations between PAHs or PAH–DNA damage and fetal growth reduction have been reported in some but not all studies (Dejmek et al. 2000; Perera et al. 1998, 2003; Sram et al. 2005). In the Czech Republic, ambient PAHs significantly increased the risk of intrauterine growth retardation (IUGR) both in Teplice and Prachatice (Dejmek et al. 2000). An earlier study in Poland found that the infants who had higher than median leukocyte PAH–DNA adduct level had significantly reduced birth weight, length, and head circumference (Perera et al. 1998). In New Jersey, USA, the risk of fetal death, premature birth, and low birth weight was significantly higher for those with a high prenatal polycyclic organic matter exposure (Vassilev et al. 2001). However, the limitations of most prior studies [retrospective or cross-sectional design, reliance on ambient air monitoring data, failure to account for co-exposure to other sources of PAHs such as environmental tobacco smoke (ETS)] have prevented definitive causal inferences regarding airborne PAHs and impaired fetal growth (Sram et al. 2005). We conducted two parallel prospective cohort studies in Krakow, Poland, and New York City (NYC), USA, using identical eligibility criteria, study design, and personal air monitoring methodology. Here we examined effects across the entire range of PAH exposure in each cohort separately, to understand the relationship between in utero exposure to airborne PAHs and fetal growth within each population. We also conducted exploratory analyses comparing the magnitude of PAH-related effects between the two different populations within the exposure range common to both, recognizing the limitations of such international, interethnic comparisons. The U.S. and Polish cohorts represent a wide range of exposure, experienced in many other urban areas; therefore, study results in Krakow and NYC are relevant to other populations worldwide. In the Krakow cohort, the average PAH concentration estimated by personal air monitoring was 39.0 ng/m3 (range, 1.8–272.2 ng/m3), compared with 3.3 ng/m3 (range, 0.3–36.5 ng/m3) in NYC. Comparable personal air monitoring data on PAHs are not available for other populations, but stationary ambient air monitoring data for BaP can be used for comparison. The mean ambient BaP level in Krakow was 3.8 ng/m3 in 2000. Annual mean ambient BaP level in various locations within Krakow ranged from 4 to 10 ng/m3 during 2002. This level is comparable to the winter means reported in Teplice (7.42 ng/m3) and Prachatice (5.37 ng/m3), Czech Republic, between 1993 and 1994 (Binkova et al. 1999) but lower than that measured in Tongliang, China, between 2002 and 2003 (15 ng/m3) (Chow et al. 2006). In an ongoing prospective study in NYC, personal exposure to BaP among the cohort of pregnant women was 0.49 ± 0.65 ng/m3 (Tonne et al. 2004). In U.S. cities, as well as in many urban areas of Europe, ambient BaP concentrations are generally < 1 ng/m3, but may range between 1 and 5 ng/m3 during winter or in areas with heavy traffic (Naumova et al. 2002; Tonne et al. 2004).

Biomarkers of exposure & effect:: validationBiomarker: cigarette Smoke: urinary cotinine, PAH Exposure: urinary 1-hydroxypyrene (1- OHP), 2-naphthol (2-NP) and 1-naphthol (1-NP) methylating chemical exposure: 7- methylguanine (7-MeG).Exposure/effect represented: PAHStudy type (in vitro, animals, humans): humansStudy design (if human): cross-sectionalStudy size (if human): 18 individualsMode of exposure (if in vivo) (acute, chronic, root of exposure): smoking cessationMethod of analysis: HPLCSensitivity (LOD): for 1-OHP 0.001μg/l, for 1 and2-NP 0.04μg/lAccuracy: for 1-OHP CV 8%, for 1 and2-NP CV 7.2%, 2.5% respectively, for 7-MeG CV 4.3%Inter-individual variation: The urinary 1-OHP levels of smokers ranged from 0.032 to 0.407, and the mean ± SD was 0.16±0.11 lg/g Cr.Dose-response: The mean levels of five markers decreased after smoking cessation by 54% (7-MeG) to 19% (1-NP). The levels of cotinine, 1-OHP, 2-NP and 7-MeG significantly decreased after smoking cessation. KEYWORDS CLASSIFICATION: analogs & derivatives;analysis;Adult;biomarkers of exposure & effect: field studies;Guanine;Humans;Hydrocarbons;Japan;Middle Aged;Polycyclic Hydrocarbons,Aromatic;Research;Smoking Cessation;urine. OBJECTIVE: Humans are exposed to various carcinogens by smoking. Urinary metabolites of polycyclic aromatic hydrocarbons (PAH), one of the major carcinogens in cigarette smoke, were measured as the environmental carcinogen exposure marker for humans. We evaluated urinary exposure markers for smoking cessation. METHOD: In this study, we measured cigarette smoke exposure markers, such as urinary cotinine, PAH exposure markers, such as urinary 1-hydroxypyrene (1-OHP), 2-naphthol (2-NP) and 1-naphthol (1-NP), as well as a methylating chemical exposure marker, 7-methylguanine (7-MeG). The before smoking cessation levels of these markers, and the after smoking cessation levels were then compared. Eighteen subjects participated in this smoking cessation program. RESULTS: Levels of all of four markers were found to have decreased by 19-54% after smoking cessation. Urinary cotinine, 1-OHP, 2-NP and 7-MeG levels were found to have significantly decreased after smoking cessation. There were positive correlations between cotinine and three urinary PAH markers and between 1-OHP, 2-NP and 7-MeG. CONCLUSION: PAH metabolites were better biomarkers of smoking cessation than 7-MeG. Analyzing urinary metabolites or urinary DNA adducts is suitable for epidemiological studies.

This study investigated host factors and environmental factors as potential determinants of polychlorinated aromatic hydrocarbons (PCAHs) in serum of adolescents. We recruited 200 participants (80 boys and 120 girls), with a mean age of 17.4 years (SD, 0.8), in Belgium from a rural control area (Peer) and from two polluted suburbs of Antwerp where a nonferrous smelter (Hoboken) and waste incinerators (Wilrijk) are located. We quantified polychlorinated biphenyls (PCBs; congeners 138, 153, and 180) in serum by gas chromatography and obtained the toxic equivalents (TEQs) of PCAHs in serum with the chemically activated luciferase gene expression bioassay (CALUX). Serum PCB concentration was higher in boys than in girls (1.67 vs. 1.02 nmol/L or 377 vs. 210 pmol/g serum lipids; p< 0.001). In the whole adolescent group, multiple regression showed that serum PCB concentration decreased 0.06 nmol/L per 1% increase in body fat content (p< 0.001) and increased 0.39 nmol/L and 0.14 nmol/L per 1 mmol/L increase in serum concentrations of triglycerides (p < 0.001) and cholesterol (p = 0.002), respectively. Host factors explained 44% of the serum PCB variance. In the same model, serum PCB concentration increased 0.14 nmol/L with 10 weeks of breast-feeding (p< 0.001) and 0.06 nmol/L with intake of 10 g animal fat per day (p < 0.001), and was associated with residence in the waste incinerator area (9% higher; p = 0.04); 11% of the variance could be explained by these environmental factors. The geometric mean of the serum TEQ value was similar in boys and girls (0.15 TEQ ng/L or 33.0 pg/g serum lipids). In multiple regression, TEQ in serum decreased 0.03 ng/L per centimeter increase in triceps skinfold (p = 0.006) and was 29% higher in subjects living close to the nonferrous smelter (p < 0.001). This study showed that in 16- to 18-year-old teenagers host factors are important determinants of serum concentrations of PCAHs, whereas environmentally related determinants may to some extent contribute independently to human exposure to these persistent chemicals in the environment. ispartof: Environmental health perspectives vol:110 issue:6 pages:583-9 ispartof: location:United States status: published

We studied the contamination level of the soils of the Sarno River basin in southwestern Italy by combined acute toxicity test with Dapnia magna and chemical extraction of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs). For the ecotoxicological assessment, 188 samples were taken and coincided with those of a previous study (2013) where heavy metals were surveyed. For the organics assessment, 21 samples were selected nearby representative areas of elevated anthropic pressure. About 10.1 % of the samples showed noticeable sign of D. magna mortality, 61-100 %, and fall along the potentially floatable areas of Sarno and Solofrana basins with high degree of contamination by Cr, As, Zn, and Hg. High levels of ecotoxicity, 61-100 %, were determined in the lower Sarno River basin in areas of moderate or low degree of contamination by Cd, Cu Hg, Pb, Sb, Sn, and Zn. Benzo(a) pyrene, indenopyrene, and benzo(g,h,i) perylene were present at concentrations of 0.32, 0.23, and 0.18 mg kg(-1), respectively, 2- to 3-fold the law limits with most of the samples falling nearby the points where the ecotoxicity output was close to 100%. Among OCPs, pp'-DDT had a mean of 0.225 mg kg(-1) and hence about more than 200- and 2-fold the residential, 0.01 mg kg(-1), and commercial/industrial limits, 0.1 mg kg(-1) and determined-mainly in the central Sarno valley in an area where elevated concentrations of benzopyrene and D. magna mortality were also observed. The study evidenced the high rate of contamination by PAHs and OCPs of the soils and the need of urgent remediation actions.

The Deepwater Horizon (DWH) oil spill in the spring of 2010 resulted in an input of ∼4.1 million barrels of oil to the Gulf of Mexico; >22% of this oil is unaccounted for, with unknown environmental consequences. Here we investigated the impact of oil deposition on microbial communities in surface sediments collected at 64 sites by targeted sequencing of 16S rRNA genes, shotgun metagenomic sequencing of 14 of these samples and mineralization experiments using 14 C-labeled model substrates. The 16S rRNA gene data indicated that the most heavily oil-impacted sediments were enriched in an uncultured Gammaproteobacterium and a Colwellia species, both of which were highly similar to sequences in the DWH deep-sea hydrocarbon plume. The primary drivers in structuring the microbial community were nitrogen and hydrocarbons. Annotation of unassembled metagenomic data revealed the most abundant hydrocarbon degradation pathway encoded genes involved in degrading aliphatic and simple aromatics via butane monooxygenase. The activity of key hydrocarbon degradation pathways by sediment microbes was confirmed by determining the mineralization of 14 C-labeled model substrates in the following order: propylene glycol, dodecane, toluene and phenanthrene. Further, analysis of metagenomic sequence data revealed an increase in abundance of genes involved in denitrification pathways in samples that exceeded the Environmental Protection Agency (EPA)'s benchmarks for polycyclic aromatic hydrocarbons (PAHs) compared with those that did not. Importantly, these data demonstrate that the indigenous sediment microbiota contributed an important ecosystem service for remediation of oil in the Gulf. However, PAHs were more recalcitrant to degradation, and their persistence could have deleterious impacts on the sediment ecosystem. © 2014 International Society for Microbial Ecology All rights reserved.

This study was conducted to investigate the evaporation ratios of polycyclic aromatic hydrocarbons (PAHs) from the food industry treatment sludge. Five PAH compounds having different ring numbers were targeted. The effects of temperature, UV and TiO2 on PAH evaporation were also studied. All applications were performed in a specially designed apparatus. The air in the apparatus was vacuumed to collect the evaporated PAHs on the PUF cartridges. Then, these PUF cartridges were extracted for determination of PAHs. The PAH concentrations were measured by a gas-chromatography mass-spectrometer (GC-MS). 91% of the initial Sigma(5) PAHs in the sludge was evaporated into the air at the end of the UV application. However, this value decreased to 21% when UV was not employed. Initial and final PAR levels in the sludge were measured to determine the removed PAHs which refer to the addition of degraded and evaporated PAHs. The results indicated that the UV-TiO2 application at high temperatures was considered an appropriate PAH removal method because it restricted the evaporation of PAHs while it removed high levels of PAHs. PAHs were mainly removed from the sludge by degradation rather than evaporation with this application.

A composite magnetic material consisting of zero-valent iron, iron oxide-oxyhydroxide and graphene was synthesized and used successfully as a sorbent for the micro solid-phase extraction of PAHs, PCBs and phthalic acid esters. The components endow the composite with multiple characteristics such as adsorption capability and facile removal due to its magnetic properties. Due to the π-π electrostatic stacking property of graphene, the high specific surface area and the adsorption capability of both components, the resulting black flaky Fe0/iron oxide-oxyhydroxide/graphene composite showed high extraction efficiency for the target analytes from water samples. Compared with the neat graphene, the composite material has improved properties in terms of microextraction capabilities as both the hydrophobic graphene and zero-valent iron participate in the adsorption of the hydrophobic molecules. The precision from the extraction of all three groups of compounds was lower than 7% and the recoveries were from 90 to 93% from a spiked lake water sample. The high recoveries in relation to the low final volume of the desorption solvent ensure high preconcentration efficiency and a promising sorbent for analytical applications. © 2012 Elsevier B.V. Journal of Chromatography A

Occupational exposures to wood dust have been associated with an elevated risk of sinonasal cancer (SNC). Wood dust is recognized as a human carcinogen but the specific cancer causative agent remains unknown. One possible explanation is a co-exposure to; wood dust and polycyclic aromatic hydrocarbons (PAHs). PAHs could be generated during incomplete combustion of wood due to heat created by use of power tools. To determine if PAHs are generated from wood during common woodworking operations, PAHs concentrations in wood dust samples collected in an experimental chamber operated under controlled conditions were analyzed. In addition, personal air samples from workers exposed to wood dust (n=30) were collected. Wood dust was generated using tree different power tools: vibrating sander, belt sander, and saw; and six wood materials: fir, Medium Density Fiberboard (MDF), beech, mahogany, oak and wood melamine. Monitoring of wood workers was carried out by means of personnel sampler device during wood working operations. We measured 21 PAHs concentrations in wood dust samples by capillary gas chromatographic-ion trap mass spectrometric analysis (GC-MS). Total PAH concentrations in wood dust varied greatly (0.24 – 7.95 ppm) with the lowest being in MDF dust and the highest in wood melamine dust. Personal exposures to PAHs observed were between 37.5-119.8 ng m-3 among workers during wood working operations. Our results suggest that PAH exposures during woodworking operation are present and hence could play a role in the mechanism of cancer induction related to wood dust exposure.

Polycyclic aromatic hydrocarbons (PAHs) likely play a role in many cancers even in never-smokers. We tried to find a model to explain the relationship between variation in PAH-related DNA adduct levels among people with similar exposures, multiple genetic polymorphisms in genes related to metabolic and repair pathways, and nucleotide excision repair (NER) capacity. In 111 randomly selected female never-smokers from the Golestan Cohort Study in Iran, we evaluated 21 SNPs in 14 genes related to xenobiotic metabolism and 12 SNPs in eight DNA repair genes. NER capacity was evaluated by a modified comet assay, and aromatic DNA adduct levels were measured in blood by32P-postlabeling. Multivariable regression models were compared by Akaike's information criterion (AIC). Aromatic DNA adduct levels ranged between 1.7 and 18.6 per 10(8) nucleotides (mean: 5.8 ± 3.1). DNA adduct level was significantly lower in homozygotes for NAT2 slow alleles and ERCC5 non-risk-allele genotype, and was higher in the MPO homozygote risk-allele genotype. The sum of risk alleles in these genes significantly correlated with the log-adduct level (r = 0.4, p < 0.001). Compared with the environmental model, adding Phase I SNPs and NER capacity provided the best fit, and could explain 17% more of the variation in adduct levels. NER capacity was affected by polymorphisms in the MTHFR and ERCC1 genes. Female non-smokers in this population had PAH-related DNA adduct levels three to four times higher than smokers and occupationally-exposed groups in previous studies, with large inter-individual variation which could best be explained by a combination of Phase I genes and NER capacity. Grant sponsor: Environmental Cancer Risk, Nutrition and Individual Susceptibility (ECNIS), a network of excellence operating within the European Union 6th Framework Program [Priority 5: ‘‘Food Quality and Safety’’]; Grant number: 513943

We have developed and validated a sandwich chemiluminescence immunoassay (SCIA) which measures polycyclic aromatic hydrocarbon (PAH)-DNA adducts combining high throughput and adequate sensitivity, appropriate for evaluation of adduct levels in human population studies. Fragmented DNA is incubated with rabbit antiserum elicited against DNA modified with r7,t8-dihydroxy-t-9,10-epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene (BPDE) and subsequently trapped by goat anti-rabbit IgG bound to a solid surface. Anti-single-stranded (ss) DNA antibodies binds in a quantity proportional to the adduct levels and is detected by chemiluminescence. The BPDE-DNA SCIA has a limit of detection of 3 adducts per 10(9) nucleotides with 5 μg DNA per well. We have validated the BPDE-DNA SCIA using DNA modified in vitro, DNA from benzo[a]pyrene (BP)-exposed cultured cells and mice. The levels of adduct measured by SCIA were lower (30-60%) than levels of bulky DNA adducts measured in the same samples by (32)P-postlabelling. The BPDE-DNA SCIA also detected adducts produced in vivo by PAHs other than BP. When blood DNA samples from maternal/infant pairs were assayed by BPDE-DNA SCIA, the adduct levels obtained were significantly correlated. However, there was no correlation between (32)P-postlabelling and SCIA values for the same samples. The SCIA can be extended to any DNA adduct and is expected to provide, when fully automated, a valuable high-throughput approach in large-scale population studies. This work was supported by contracts from the European Union (to S.A.K): Network of Excellence ECNIS—‘Environmental cancer risk, nutrition and individual susceptibility’ and Integrated Project NewGeneris—‘Newborns and genotoxic exposure risks’ (contract numbers FOOD-CT-2005-513943, FOOD-CT-2005-016320). The work was also supported in part by the intramural program of the Center for Cancer Research, National Cancer Institute, National Institutes of Health, Bethesda, MD, USA (to M.C.P.).

Background Particulate matter (PM) has been associated to adverse health effects in exposed population and DNA damage has been extensively reported in in vitro systems exposed to fine PM (PM2.5). The ability to induce gene expression profile modulation, production of reactive oxygen species (ROS) and strand breaks to DNA molecules has been investigated in A549 cells exposed to winter and summer Milan PM2.5. Results A549 cells, exposed to 10 μg/cm 2 of both winter and summer PM2.5, showed increased cytotoxicity at 24 h and a significant increase of ROS at 3 h of treatment. Despite these similar effects winter PM induced a higher number of gene modulation in comparison with summer PM. Both PMs modulated genes related to the response to xenobiotic stimuli (CYP1A1, CYP1B1, TIPARP, ALDH1A3, AHRR) and to the cell – cell signalling (GREM1) pathways with winter PM2.5 inducing higher fold increases. Moreover the winter fraction modulated also JUN ( cell – cell signalling ), GDF15, SIPA1L2 ( signal transduction ), and HMOX1 ( oxidative stress ). Two genes, epiregulin (EREG) and FOS-like antigen1 (FOSL1), were significantly up-regulated by summer PM2.5. The results obtained with the microarray approach have been confirmed by qPCR and by the analysis of CYP1B1 expression. Comet assay evidenced that winter PM2.5 induced more DNA strand breaks than the summer one. Conclusion Winter PM2.5 is able to induce gene expression alteration, ROS production and DNA damage. These effects are likely to be related to the CYP enzyme activation in response to the polycyclic aromatic hydrocarbons (PAHs) adsorbed on particle surface.

Polycyclic aromatic hydrocarbons (PAH) are an important class of environmental contaminants many of which require metabolic activation to DNA-reactive bay or fjord region diolepoxides (DE) in order to exert their mutagenic and carcinogenic effects. In this study, the mutagenicity of the bay region diolepoxides (+)-anti-7,8-dihydroxy-9,10-epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene (BPDE) and (±)-anti-1,2-dihydroxy-3,4-epoxy-1,2,3,4-tetrahydrodibenzo[a,h]anthracene (DBADE) and the fjord region diolepoxides (±)-anti-11,12-dihydroxy-13,14-epoxy-11,12,13,14-tetrahydrodibenzo[a,l]-pyrene (DBPDE) and (±)-anti-3,4-dihydroxy-1,2-epoxy-1,2,3,4-tetrahydrobenzo[c]-phenanthrene (BPhDE) was compared in nucleotide excision repair (NER) proficient and deficient hamster cell lines. The (32)P-postlabelling assay was applied to analyze DNA adduct levels and the Hprt gene mutation assay for monitoring mutations. Previously, we found that the mutagenicity per adduct was four times higher for DBPDE compared to BPDE in NER proficient cells. In these same cells, the mutagenicity of DBADE and BPhDE adducts was now found to be significantly lower compared to that of BPDE. In NER deficient cells the highest mutagenicity per adduct was found for BPDE and there was a tenfold and fivefold difference when comparing the BPDE data with the DBADE and BPhDE data, respectively. In order to investigate to what extent the mutagenicity of the different adducts in NER proficient cells was influenced by repair or replication bypass, we measured the overall NER incision rate, the rate of adduct removal, the rate of replication bypass and the frequency of induced recombination in the Hprt gene. Since NER turned out to be an important pathway for the yield of mutations, we further analyzed the role of transcription coupled NER versus global genome NER. However, our data demonstrate that neither of these pathways seems to be the sole factor determining the mutation frequency of the four PAH-DE and that the differences in the repair efficiency of these compounds could not be related to the presence of a bay or fjord region in the parent PAH. This work was supported by The European Commission; projects AMBIPAH (QLK4-CT-2002-02402), DIEPHY (FOOD-CT-2003-505609), ECNIS (FOOD-CT-2005-513943) and The Swedish Research Council Formas.

Historical records of total organic carbon (TOC), black carbon (BC), and polycyclic aromatic hydrocarbons (PAHs) were reconstructed in dated sediment cores from four nearby lakes in central Switzerland. In the sub-Alpine Lake Thun, located at 558 m a.s.l., the proximity to anthropogenic emission sources is reflected in higher input of BC and PAHs into sediments with fluxes only slightly decreasing during the last decades. PAH/BC ratios are relatively high and correlation between levels of total PAHs and BC is almost inexistent in Lake Thun, probably due to the presence of less condensed forms of the BC spectrum (char BC) that is underestimated with the chemothermal oxidation method applied in this study. The sediment profiles of TOC, BC, and PAHs are noticeably different in the mountain lakes located around 2000 m a.s.l. In Lake Engstlen, the PAH/BC ratios, as well as the correlation between PAHs and BC, point towards appreciable amounts of predominantly light soot particles. Light soot particles have higher mobility and can, therefore, be efficiently transported to this remote site. The proglacial Lake Oberaar is shown to be a receptor of BC and PAHs released by the fast melting adjacent glacier acting as a secondary source for these conservative species temporarily stored in the glacier ice. Finally, Lake Stein is in strong contrast to all other lakes. High flux of BC into Lake Stein, combined with constant temporal evolutions of BC and PAHs, and in particular BC/TOC ratios approaching 100% are all strong indications for a geogenic presence of graphite in its catchment area.

A phenyl-based hybrid organic -inorganic coating has been synthesized and processed by hard X-ray lithography. The overall lithography process is performed in a two-step process only (X-rays exposure and chemical etching). The patterns present high aspect ratio, sharp edges, and high homogeneity. The coating has been doped with a variety of polycyclic aromatic hydrocarbon functional molecules, such as anthracene, pentacene, and fullerene. For the first time, hard X-rays have been combined with thick hybrid functional coatings, using the sol-gel thick film directly as resist. A new technique based on a new material combined with hard X-rays is now available to fabricate optical devices. The effect due to the high-energy photon exposure has been investigated using FT-IR and Raman spectroscopy, laser scanner, optical profilometer, and confocal and electron microscope. Highquality thick hybrid fullerene-doped microstructures have been fabricated. © 2011 American Chemical Society.

Cholinesterase (ChE) and ethoxyresorufin-O-deethylase (EROD) were of special interest to this study as these biochemical tools have been widely used for the determination of exposure to pollutants. In this study, the freshwater oligochaete Limnodrilus profundicola was tested for its potential as a bioindicator of freshwater pollution. For this purpose, the ChE and EROD activities of L. profundicola and the level of polycyclic aromatic hydrocarbons (PAH) of water samples collected from different sites along the Curuksu stream on the Menderes River (the ancient Meander) running through south-western Turkey were studied. First, these activities were characterized using, as model substrates, acetylthiocholine (ATC), propionylthiocholine (PTC), and butyrylthiocholine (BTC). Then, the in vivo effects of insecticides and pollutants on these activities were investigated. L. profundicola were exposed to various doses of methyl-parathion, methomyl, and deltamethrin. Although significant inhibition of ChE was detected with each of the insecticides, the highest level of inhibition was observed with methyl-parathion. In addition to the inhibition of ChE, the activity of EROD was induced by exposure to oil-contaminated sediments. Thus, although L. profundicola has a reputation for being very resistant to pollution (although it is not insensitive to it), we demonstrated that it may potentially be used as a bioindicator species for contaminant exposure when ChE and EROD are used as biomarkers. © 2010 Wiley Periodicals, Inc.

This study was undertaken to determine the possibility of potential impact of PAHs on the aquatic biota. First, we had developed a new method for measuring 13 different priority pollutant PAHs in waste water samples. Then, eight different water samples collected from different sites along the Menderes River were analysed by this method involving SPE extraction and reverse-phase HPLC. The method presented here is suitable for rapid and accurate determination of PAH in surface waters and the PAH recoveries are practically quantitative. The levels of PAH in the analyzed samples range from 1.8 μg/L to 24.9 μg/L and industrialized areas were found to be highly polluted. © 2011 Springer Science+Business Media, LLC.

Biphenylketones were identified as novel inhibitors of NFκB activation. Structure–activity studies led to the identification of compound 4c, which had good potency against osteoclasts (IC50 = 0.8 μM), showed oral activity, and was able to completely prevent inflammation and bone loss in vivo.

Background Polycyclic aromatic hydrocarbons (PAHs) are toxic, widely-distributed, environmentally persistent, and carcinogenic byproducts of carbon-based fuel combustion. Previously, plant studies have shown that PAHs induce oxidative stress, reduce growth, and cause leaf deformation as well as tissue necrosis. To understand the transcriptional changes that occur during these processes, we performed microarray experiments on Arabidopsis thaliana L. under phenanthrene treatment, and compared the results to published Arabidopsis microarray data representing a variety of stress and hormone treatments. In addition, to probe hormonal aspects of PAH stress, we assayed transgenic ethylene-inducible reporter plants as well as ethylene pathway mutants under phenanthrene treatment. Results Microarray results revealed numerous perturbations in signaling and metabolic pathways that regulate reactive oxygen species (ROS) and responses related to pathogen defense. A number of glutathione S-transferases that may tag xenobiotics for transport to the vacuole were upregulated. Comparative microarray analyses indicated that the phenanthrene response was closely related to other ROS conditions, including pathogen defense conditions. The ethylene-inducible transgenic reporters were activated by phenanthrene. Mutant experiments showed that PAH inhibits growth through an ethylene-independent pathway, as PAH-treated ethylene-insensitive etr1-4 mutants exhibited a greater growth reduction than WT. Further, phenanthrene-treated, constitutive ethylene signaling mutants had longer roots than the untreated control plants, indicating that the PAH inhibits parts of the ethylene signaling pathway. Conclusions This study identified major physiological systems that participate in the PAH-induced stress response in Arabidopsis. At the transcriptional level, the results identify specific gene targets that will be valuable in finding lead compounds and engineering increased tolerance. Collectively, the results open a number of new avenues for researching and improving plant resilience and PAH phytoremediation.

This study was carried out to investigate the concentrations and potential sources of the polycyclic aromatic hydrocarbons (PAHs) in sludge of 14 wastewater treatment plants (WWTPs). Sludge samples were collected from 2 municipal WWTPs, 11 industrial WWTPs, and 1 sanitary landfill leachate treatment plant within the city of Bursa, Turkey during the summer of 2008. Ultrasonication was applied for extraction and gas chromatography-mass spectrometry was used to analyze the PAH contents of the samples. Twelve of the 16 EPA-listed PAH compounds were determined. Total PAH concentrations (Sigma(12) PAHs) determined in all of the sludge samples ranged from 1,781 to 19,866 microg/kg dry matter (dm). The sum of 8 of the 11 EU PAHs varied between 1,481 and 17,314 microg/kg dm, and 3 of the samples exceeded the proposed EU limit for land application. One of the automotive industry sludges contained the highest level of PAHs, followed by one of the municipal sludges. The average sum of 5- and 6-ring PAH compounds in all of the sludge samples amounted to almost 65% of the total PAHs. The diagnostic ratios of specific PAHs were calculated to determine the dominant sources for the PAHs in the sludge samples.

Aromatic compounds such as polycyclic aromatic hydrocarbons, arylamines and heterocyclic amines require metabolic activation to form metabolites able to bind to DNA, a process mediated by polymorphic enzymes. We measured aromatic DNA adducts in white blood cells by the (32)P-post-labelling assay in a sample of 296 healthy adults (147 men and 149 women) from five regions of Spain. We also analyzed functional polymorphisms in the metabolic genes CYP1A1, CYP1A2, EPHX1, GSTM1, GSTT1, NAT2 and SULT1A1. A significant increased level of DNA aromatic adducts was found related to the fast oxidation-hydrolysis phenotype defined by the polymorphism I462V in CYP1A1, the allele A in IVS1-154C>A of CYP1A2 and the combination Tyrosine-Arginine for Y113H and H139R of EPHX1. Geometric means (adducts per 10(-9) normal nucleotides) were 2.17, 4.04 and 6.30 for slow, normal and fast phenotypes, respectively (P-trend = 0.01). Slow acetylation by NAT2 was associated with a significant decrease in adduct level; subjects with slow alleles *5A and *7A/B had in average 1.56 x 10(-9)adducts, as compared with 5.60 for those with normal NAT2 activity (P-value = 0.01). No association was seen with polymorphisms of other metabolic genes such as GSTM1, GSTT1 or SULT1A1. We concluded that the metabolic pathways of oxidation, hydrolysis and acetylation are relevant to the formation of bulky DNA adducts. This could suggest a potential involvement of aromatic compounds in the formation of such adducts; however, given lack of specificity of the post-labeling assay, a firm conclusion cannot be drawn. European Commission (SO 97 200302 05F02); Spanish Ministry of Health (Exp. 02-0652); Red Tema´tica de Investigacio´n Cooperativa de Centros de Ca´ncer (C03/10); Regional Governments; International Agency for Research on Cancer (AEP/93/02); Institut d’Investigacio´ Biome`dica de Bellvitge (R.I.); Environmental Cancer Risk, Nutrition and Individual Susceptibility, a Network of Excellence of the 6th EU Framework Program (FP6, FOOD-CT-2005-513 943 to A.A., C.A.G., N.S., G.C.).

Air pollution in Milan causes health concern due to the high concentrations of particulate matter (PM10 and PM2.5). The aim of this study was to investigate possible seasonal differences in PM10 and PM2.5 chemical composition and their biological effects on pro-inflammatory cytokine release and cytotoxicity. The PM was sampled during winter and summer seasons. The winter PMs had higher levels of PAHs than the summer samples which contained a greater amount of mineral dust elements. The PM toxicity was tested in the human pulmonary epithelial cell lines BEAS-2B and A549. The winter PMs were more cytotoxic than summer samples, whereas the summer PM10 exhibited a higher pro-inflammatory potential, as measured by ELISA. This inflammatory potential seemed partly due to biological components such as bacterial lipopolysaccharides (LPS), as evaluated by the use of Polymixin B. Interestingly, in the BEAS-2B cells the winter PM2.5 reduced proliferation due to a mitotic delay/arrest, while no such effects were observed in the A549 cells. These results underline that the in vitro responsiveness to PM may be cell line dependent and suggest that the PM different properties may trigger different endpoints such as inflammation, perturbation of cell cycle and cell death.