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Individual sugars, organic acids, total polyphenols, vitamin C and antiradical activity (as measured by DPPH method) were quantified in cultivated Fragaria vesca berries, comparing different varieties (Regina delle Valli, Alpine, Sara and Valitutto) and different environments with regard to altitude. Cultivar effect mainly influenced the concentration of total polyphenols and antiradical activity which are strongly correlated (R2 = 0.91; P = 0.001); conversely, altitude seemed to exert an influence in sugar and organic acid composition. The comparison of the general quality of the most diffused cultivar of F. vesca (Regina delle Valli and Alpine) evidenced that both cultivars have the same nutritional properties, whereas Regina delle Valli is better than Alpine from the point of view of total polyphenolic content (716 vs 471 mg catechin/100 g fresh weight) and radical scavenging activity (301 vs 219 ml DPPH solution/100 g fresh weight), thus resulting more attractive from the health protecting attributes point of view. F. vesca berries showed also a concentration of sugars, citric acid, malic acid and total polyphenols much higher than those reported in literature for Fragaria x ananassa.

A high activity α-carbonic anhydrase (CA, EC 4.2.1.1) has been purified from various tissues of the Antarctic seal Leptonychotes weddellii. The new enzyme, denominated lwCA, has a catalytic activity for the physiologic CO(2) hydration to bicarbonate reaction, similar to that of the high activity human isoform hCA II, with a k(cat) of 1.1×10(6) s(-1), and a k(cat)/K(m) of 1.4×10(8) M(-1) s(-1). The enzyme was highly inhibited by cyanate, thiocyanate, cyanide, bicarbonate, carbonate, as well as sulfamide, sulfamate, phenylboronic/phenylarsonic acids (K(I)s in the range of 46-100 μM). Many clinically used sulfonamides, such as acetazolamide, methazolamide, dorzolamide, brinzolamide and benzolamide were low nanomolar inhibitors, with K(I)s in the range of 5.7-67 nM. Dichlorophenamide, zonisamide, saccharin and hydrochlorothiazide were weaker inhibitors, with K(I)s in the range of 513-5390 nM. The inhibition profile with anions and sulfonamides of the seal enzyme was rather different from those of the human isoforms hCA I and II. The high sensitivity to bicarbonate inhibition of lwCA, unlike that of the human enzymes, may reflect an evolutionary adaptation to the deep water, high CO(2) partial pressure and hypoxic conditions in which Weddell seals spend much of their life.

Changes in tannins, ascorbic acid and sugars in astringent persimmons ‘Rojo Brillante’ and ‘Kaki Tipo’ were investigated during fruit maturation and after postharvest treatments. Soluble tannins exhibited a significant initial increment, followed by a marked constant decrease that led to values between 0.2 and 0.3 g/100 g fresh weight (FW) in the last stage of maturity studied. During the entire period monitored, insoluble tannins represented the minor component of the total tannic fraction, accounting for 9–27% (Rojo Brillante) and 17–32% (Kaki Tipo) of total tannins; levels of insoluble tannins were comparable to or higher than the soluble tannins in softer fruits. Total vitamin C decreased from 0.18–0.20 to about 0.08 g/100 g FW during fruit development owing to fruit growth rather than to degradation processes. Total sugars increased from about 4 g/100 g FW at the early stage of fruit development to 17 g/100 g FW after reaching the commercial stage of maturity. Glucose and fructose increased during the entire period monitored, while sucrose reached a maximum and then gradually decreased, probably owing to a strong invertase activity. Antiradical activities were significantly related to the corresponding tannic fraction. In both ‘Rojo Brillante’ and ‘Kaki Tipo’, postharvest treatment with CO 2 was more effective than with ethylene in reducing soluble tannin concentration (0.031–0.067 and 0.220–0.262 g/100 g FW, respectively).

Sea surface microlayer (SML) and sea water samples (SSW) collected in the Gerlache Inlet Sea (Antarctica) were analysed for n-alkanes and polycyclic aromatic hydrocarbons (PAHs). The SML is a potential enrichment site of hydrophobic organic compounds compared to the underlying water column. Total concentration ranges of n-alkanes and PAHs (dissolved and particulate) in subsurface water (− 0.5 m depth) were 272–553 ng l − 1 (mean: 448 ng l − 1 ) and 5.27–9.43 ng l − 1 (mean: 7.06 ng l − 1 ), respectively. In the SML, the concentration ranges of n-alkanes and PAHs were 353–968 ng l − 1 (mean: 611 ng l − 1 ) and 7.32–23.94 ng l − 1 (mean: 13.22 ng l − 1 ), respectively. To evaluate possible PAH contamination sources, specific PAH ratios were calculated. The ratios reflected a predominant petrogenic input. A characterisation of surface active substances was also performed on SML and SSW samples, both by gas bubble extraction, and by dynamic surface tension measurements. Results showed a good correlation between n-alkanes, PAHs and refractory organic matter.

In the framework of the Italian Research Programme in Antarctica (PNRA) an oceanographic cruise was carried out between December 2000 and February 2001 in the Western Ross Sea. n -Alkanes and PAHs concentrations were analysed in sea-water samples collected at different depths at four sites (D, B, CA2, and CA). Vertical profiles of pressure, temperature, salinity and fluorescence were also performed in order to distinguish the water masses present in the sampling areas. n -Alkanes concentrations were consistent with those found in the same area during previous expeditions and showed higher values in the particulate due to the low temperatures. n -Alkanes profiles exhibited different features in the dissolved and particulate phases. The dissolved phase was characterised by a bimodal distribution with two maxima at C16 and C24 and prevalent compounds in the range C15–C32 whereas particulate was strongly dominated by long chain n -alkanes C23–C34 with C24 (Site B, CA and CA2) or C32 (Site B) as Cmax. CPI values and Pr/Ph ratios suggested a prevalent biogenic origin for aliphatic hydrocarbons. n -Alkanes vertical distributions were affected by the dynamic of the pack-ice melting and phytoplankton activity as well by the chemical–physical properties of water masses. Higher n -alkanes values were found in the High Salinity Shelf Waters (HSSW), lower n -alkanes values were found in the Antarctic Surface Waters (AASW) and Modified Circumpolar Deep Water (MCDW). The low PAHs concentration levels confirmed the still pristine character of the Antarctic environment. Neither particular trend in total PAHs concentrations along the water column and nor correlations with the most characteristic water masses of the investigated area of the Ross Sea were observed, except that total PAH higher concentrations were generally observed in correspondence of HSSW.

The occurrence of POPs in remote areas, such as Antarctica, is the result of their ability to udergo Long Range Transport (LRT) in the atmosphere, precipitation and cold condensation. In this study, both recent levels of various POPs in Trematomus bernacchii and their changes in roughly three decades were determined in order to evaluate trends of POPs in Antarctic benthic seawaters. In fact, Trematomus bernacchii is considered a good sentinel bio-indicator for monitoring not only the extent of contamination by POPs in the Antarctic aquatic ecosystem, but also changes in Antarctic ecosystem quality and trends. A slight decreasing PCB trend was detected during 30-years time span (from early 1980's to 2010) in the circumantarctic seawaters. Two higher peaks of concentrations were reported in 2001 and 2005 in the Ross Sea and they may reflect the ice melting of icebergs. Because fire risk is very high in Antarctica due to the very dry air, a large use of flame retardants in buildings and furniture of stations is highly probable; moreover, many stations were built when there were no restrictions on flame retardants use. The PBDE levels in the T. bernacchii from 2001 to 2011 ranged 0.05-0.35 pg/g and were of the same order of magnitude in 2001/2011 and in 2002/2005, with a maximum value in 2005 (0.35 pg/g). Comparable concentrations of HCB, HCHs PCDDs and PCDFs are available only for few seasons: all these compounds showed a decreasing temporal trends and their concentrations were one or more order of magnitude lower in 2000s-2010s.

Human milk samples were collected from 67 mothers in 2014 at a Primary Care Centre in Murcia (Spain) and analyzed for perfluorinated carboxylic acids (PFCAs). Concentrations measured for perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA) and perfluorododecanoic acid (PFDoDA) ranged from

The present study aims to assess the arsenic (As) levels into dust samples and its implications for human health, of four ecological zones of Pakistan, which included northern frozen mountains (FMZ), lower Himalyian wet mountains (WMZ), alluvial riverine plains (ARZ), and low lying agricultural areas (LLZ). Human nail samples (N=180) of general population were also collected from the similar areas and all the samples were analysed by using ICP-MS. In general the higher levels (p0.05) in paired dust and human nail samples were observed from ARZ and LLZ than those of other mountainous areas (i.e., WMZ and FMZ), respectively. Current results suggested that elevated As concentrations were associated to both natural, (e.g. geogenic influences) and anthropogenic sources. Linear regression model values indicated that As levels into dust samples were associated with altitude (r(2)=0.23), soil carbonate carbon density (SCC; r(2)=0.33), and population density (PD; r(2)=0.25). The relationship of paired dust and nail samples was also investigated and associations were found for As-nail and soil organic carbon density (SOC; r(2)=0.49) and SCC (r(2)=0.19) in each studied zone, evidencing the dust exposure as an important source of arsenic contamination in Pakistan. Risk estimation reflected higher hazard index (HI) values of non-carcinogenic risk (HI1) for children populations in all areas (except FMZ), and for adults in LLZ (0.74) and ARZ (0.55), suggesting that caution should be paid about the dust exposure. Similarly, carcinogenic risk assessment also highlighted potential threats to the residents of LLZ and ARZ, as in few cases (5-10%) the values exceeded the range of US-EPA threshold limits (10(-6)-10(-4)).

Siloxane-based compounds are widely used in personal care, pharmaceutical and household products as well as in industrial applications. Among the wide variety of these chemicals, special attention has been given to volatile methylsiloxanes (VMSs). These compounds have been extensively detected in several environmental compartments, as they are not effectively removed from wastewater and may migrate through different matrices and being lipophilic, bioaccumulate and biomagnify in living organisms. In this work, a prioritisation methodology for several VMSs in different environmental matrices was applied, estimating a hazard quotient by combining exposure evaluation through measured or predicted environmental concentrations (MEC or PEC) and effects using ecotoxicity data to establish no effect concentrations (PNEC). VMSs show quite different hazard potentials in the environment: for linear VMSs it is not considerable, while for cyclic VMSs the hazard is disperse. D4 and D5 may have adverse effects in water, as well as D5 and D6 in sediments. This first multi-matrix approach for the prioritisation of VMSs sets the ground for more accurate studies in the future, provided that more field-based data are reported.

This study aimed to assess the occurrence, distribution and dietary risks of seven dl-PCBs (dioxin-like PCBs) in eleven collected fish species from Chenab river, Pakistan. ∑7dl-PCBs (ng g(-1), wet weight) burden was species-specific and the maximum average concentrations were found in Mastacembelus armatus (5.43), and Rita rita (5.1). Correlation of each dl-PCBs with δ(15)N%, indicated a food chain accumulation process of these chemicals into Chenab river, Pakistan. Species-specific toxicity of each dl-PCBs (WHO-PCBs TEQ) was calculated and higher values were found in three carnivore fish species i.e., M. armatus (2.5 pg TEQ g(-1)), R. rita (2.47 pg TEQ g(-1)), Securicola gora (2.98 pg TEQ g(-1)) and herbivore fish species i.e., Cirrhinus mrigala (2.44 pg TEQ g(-1)). The EDI (Estimated Daily Intake) values in most cases exceeded the WHO benchmark (4 pg WHO-TEQ kg(-1) bw d(-1)) evidencing a potential health risk for consumers via fish consumption from Chenab river.

The aim of this study was to evaluate the effect of traffic related polycyclic aromatic hydrocarbons (PAHs) on blood parameters of subjects, including traffic police officers (TP), drivers (DR) and control subjects (CN) with presumably different levels of exposure. We quantified the urinary 1-hydroxypyrene (1-OHPyr), α-naphthol and β-naphthol (α- and β-naph) as biomarkers of exposure to PAHs in relation with biomarkers of effect (Hb, MCV, PCV, PLT, RBCs), biomarkers of inflammation/infection (CRP, WBCs), oxidative stress (SOD) and oxidative DNA damage i.e. 8-hydroxy-2-deoxyguanosine (8-OHdG). Results showed that mean 1-OHPyr, α-naph and β-naph concentrations were significantly higher in TPs (0.98, 1.55, and 1.9µmolmol-Cr(-1), respectively, p

The increased concerns with the toxic effects of chemicals have led to the necessity of monitoring pollution levels into the different environmental compartments. Thus, in order to fulfill the increasing request of rapid analysis of environmental samples, electrochemical biosensors have been proposed as reliable, fast and inexpensive devices for the analysis of pollutants. Biosensors combine the selectivity of the biomolecular reactions with operational simplicity. Enzymes have found widespread use as sensing elements in catalytic electrochemical biosensors. Enzymes are also used in affinity biosensors, as label of the biorecognition event. The successful use of enzymes is essentially due to their specificity and to their ability to convert single biorecognition events into a multitude of detectable molecules. In this work, the use of enzymes for the development of both catalytic and affinity biosensors for the detection of environmental pollutants is described. In particular, different strategies for the development of catalytic, esterase-based biosensors for the detection of organophosphorous and carbamate pesticides, recently proposed by the author's lab, will be revised. Moreover, preliminary results regarding the development of an emerging class of environmental pollutants, i.e. PBDEs, by means of an affinity biosensor will be also presented.

The aim of this study was to evaluate and compare the exposure of household women and professional male workers to combustion emission in the indoor and semi-outdoor environments, respectively, by using biochemical parameters and the biomarkers of exposure to polycyclic aromatic hydrocarbon (PAH). Female (WR n = 60) and male "cooks" (WC n = 60) exposed to the combustion emission of fuel wood and coal in rural/suburban areas of Pakistan were recruited in this study and compared to non-exposed female (CF) and male (CM) groups (n = 32 and 34, respectively). Urinary biomarkers of PAH exposure including 1-hyroxypyrene (1-OHPyr), α-naphthol, and β-naphthol were analyzed together with the biomarkers of effect, including the serum c-reactive proteins (CRP), white blood cells (WBCs), hemoglobin (Hb), red blood cells (RBC), and platelet (PLT) count. In addition, blood superoxide dismutase (SOD) and urinary level of 8-hydroxydeoxyguanosine (8-OHdG) were evaluated to determine the oxidative stress and DNA damage, respectively. A questionnaire was used to document demographic-, health-, and exposure-related information. The results showed that urinary β-naphthol was almost 44% higher in WR subjects than WC (median 7.69 vs. 3.39 μmol/mol-Cr, respectively; p = 0.01) and respective controls (CF). Higher urinary 8-OHdG were observed in WR (71.1 ng/mg-Cr) than WC (56.37 ng/mg-Cr) (p 0.001), and lower life status and higher degree of headache were observed in WR than WC. In WCs, however, a low Hb and high WBC (8.29 × 10(3) μL(-1), ranging between 6.1 and 10.6 × 10(3) μL(-1)) were observed in comparison with CM. The study shows that WC subjects used larger amount of fuel and were subjected to prolonged exposure. It was concluded that the role of ventilation is fundamental and WR were more exposed to PAHs despite the fact that WC spent more time in cooking (due to occupational requirement) than WR.

This study presents the analyses of urinary biomarkers (1-OHPyr, α- and β-naphthols) of polycyclic aromatic hydrocarbons (PAHs) exposure and biomarkers of effect (i.e. blood parameters) in petroleum-refinery workers (RFs) and auto-repair workers (MCs). Exposed subjects had higher concentrations of white blood cell (WBC) count than control subjects (CN) subjects (5.31 × 103 μL−1 in exposed vs. 5.15 × 103 μL−1 in CN subjects), while the biomarker of oxidative DNA damage (8-OHdG) was significantly higher in MCs. The exposure among these two cohorts could be influenced by the ambience of the workplaces; in fact, MCs’ shops are relatively damp and enclosed workplaces in comparison with the indoor environment of refineries. PAHs in the dust samples from mechanical workshops probably originated from mixed sources (traffic exhaust and petroleum spills), while the incremental lifetime cancer risk (ILCR) for MCs showed moderate-to-low cancer risk from exposure to dust-bound PAHs. The study shows that increasing PAH exposure can be traced in MC workstations and needs to be investigated for the safety of public health.

The influence of salt concentration in the seawater on solar orientation in Talitrus saltator and Talorchestia ugolinii was studied in a confined environment (transparent plexiglass bowls). Sodium and calcium concentrations strongly affect both sea-land orientation and the sun compass mechanism in T.saltator, whereas the behaviour of T. ugolinii is less influenced. The absence of Na(+) does not influence the sun compass mechanism, but causes an inversion in the mean direction of orientation in T. saltator. In T. ugolinii, there was no influence on the compass mechanism for solar orientation and no inversion in the directional choice. In the absence of Ca(2+), a photonegative tendency was observed for T saltator together with marked reduction in the capacity to go in any direction. However, the effect of Ca(2+) absence on the orientation capacity of T. saltator is reversible and the orientation capacity can be reduced in a few minutes. The different behaviour of the two species of sandhoppers is discussed.

In this study, the occurrence and concentrations of PAHs in dust samples, which were collected from the traffic police cabins/working spots, located on the main busy roads of Lahore (TP-L) and Rawalpindi (TP-R) cities (Punjab province, Pakistan) and from the public transport vehicles in the same cities (named as AM-L and AM-R, respectively) were determined. The mean and median concentrations of ∑PAHs were observed in the following descending order: AM-L (1340 and 774 ng g(-1) d.w., respectively), TP-L (866 and 854 ng g(-1) d.w.), TP-R (504 and 379 ng g(-1) d.w.), and AM-R (393 and 290 ng g(-1) d.w. Source apportionment of the soil/dust-bound PAHs was also performed. In all the sampling areas, the diagnostic ratios, principal component analysis (PCA) followed by multiple linear regression (MLR) analysis indicated signatures of mixed sources of PAHs (including vehicular exhaust emission, gasoline/diesel, and coal/wood combustion). Estimated results of incremental lifetime cancer risk (ILCR) indicated that the traffic policemen and drivers, especially those in the urban area of Lahore, were at high risk of cancer via routes of dust ingestion and dermal contact. The results of this research could be very useful for the local Government in order to control the exposure and promote actions to alleviate PAH contamination and to manage health both at work places in the big cities of Pakistan.

Air, seawater, sea ice, and snow were collected during the austral winter (September-October 2001) and summer (January-February 2002) along the Western Antarctic Peninsula. Hexachlorobenzene (HCB)heptachloralpha- and gamma-hexachlorocyclohexane (HCH) and heptachlor epoxide, were the most frequently detected organochlorine pesticides in air. HCB and HCH levels declined over the past 20 years, with a half-life of 3 years for sigmaHCH in Antarctic air. However, heptachlor epoxide levels have not declined in Antarctic air over the past decade, possibly due to continued use of heptachlor in the southern hemisphere. Peak heptachlor concentrations in air were measured coincident with air masses moving into the region from lower latitudes. Levels of lindane were 1.2-200 times higher in annual sea ice and snow compared to alpha-HCH, likely due to greater atmospheric input of gamma-HCH. The ratio of alpha/gamma-HCH in Antarctic air, sea ice and snow was1, illustrative of a predominance of influx of lindane versus technical HCH to the regional environment. However, alpha/gamma-HCH in seawater was1, likely due to more rapid microbial degradation of gamma- versus alpha-HCH. Water/air fugacity ratios for HCHs demonstrate continued atmospheric influx of HCHs to coastal Antarctic seas, particularly during late summer.

To test the potential for using stable isotope fractionation to examine the atmospheric transport of semivolatile organic compounds (SOCs), we conducted simplified distillation experiments in the laboratory and a tracer-release experiment using mixtures of stable isotope-labeled (D and 13C) and unlabeled SOCs. Perdeuterated phenanthrene and alpha-hexachlorocyclohexane were transported more slowly via air-water gas exchange in our laboratory experiments, resulting in significant isotope fractionation of perdeuterated/unlabeled compound mixtures. In contrast, isotope fractionation of 13C6-labeled SOCs was much lower. A field tracer-release study was then conducted by spiking a seawater retention pond with a mixture of D10-labeled, 13C2-labeled, and unlabeled phenanthrene and examining isotope fractionation of the mixture after air-water gas exchange. No preferential fractionation of D10-vs 13C2-labeled phenanthrene was observed in the pond water; however, greater fractionation of D10-vs 13C2-labeled phenanthrene was observed in air samples collected within a 1-100 m radius of the pond. Thus, stable isotope tracers may provide a means of examining the atmospheric transport and air-earth exchange rates of POPs in an environmental realistic setting.

This study reports the characterization of n-alkanes and PAHs in 13 PM10 samples collected in the South area of Prato (Italy) during the period April-July 2002. n-Alkanes concentrations ranged between 9, 45 and 182, 64 ng/mc while PAHs concentrations ranged from 3, 058 to 22, 048 ng/mc. No correlation was evidenced between benzo(a)pirene and PM10 concentrations. Total carbonaceous aerosol was also measured and it meanly accounted for 21, 5% of the PM10 mass ranging from 12, 4% to 27, 1%.

Atmospheric aerosols were collected during the period from May 2000 through January 2001 at 13 different sites in and around the Baciacavallo sewage treatment plant in Prato (Italy). The urban area surrounding the plant contains significant textile industrial activity and a main arterial road. Aerosol-associated n -alkane, polycyclic aromatic hydrocarbon (PAH), nonylphenol (NP) and nonylphenolethoxylate (NPnEO) ( n =1–3) concentrations were measured in order to evaluate contributions from the sewage treatment plant, naturally produced aerosols, transportation and industrial activities to the air quality in the vicinity of the sewage treatment plant. Aerosol-associated n -alkane concentrations ranged from 36.7 to 205 ng/m 3 and their possible origin was determined by the presence of typical petroleum characteristics such as the unresolved complex mixture and an odd/even carbon ratio (Carbon Preference Index). PAH concentrations ranged from 0.855 to 24.2 ng/m 3 , in accordance with those generally found for urban aerosols in Europe. NP and NPnEO ( n =1–3), as well as fine aerosol particulate matter (PM 10 ) were significantly correlated with relative wind direction with increased levels observed in the ambient atmosphere when the relative wind direction was from the Baciacavallo sewage treatment plant. This study confirms the use of NP and NPnEO ( n =1–3) as markers of sewage treatment emissions and the importance of the contribution of aerosols produced by sewage treatment plant aeration tanks to the local atmospheric composition.

Aims of this study were to provide firsthand data on the incidence of trace metals in human seminal plasma and find possible correlations between levels of toxic metals and semen quality of Pakistani population. Human semen samples were collected from male partners of couples undergoing infertility assessment at the National Institute of Health Islamabad (Pakistan). We investigated seventy-five seminal plasma samples, which were further categorized into three groups (normozoospermia, oligozoospermia and azoospermia) according to WHO guidelines. The concentration of 17 different toxic metals in human seminal plasma was determined simultaneously by using Inductively coupled plasma mass spectrometry (ICP-MS). Out of 17 trace metals, Cd and Ni showed significant difference (p

Many epidemiological studies from all over the world have reported that populations of rural and urban environments differ in their health issues due to the differences in the countrywide pollution pattern. In developing countries, various occupational cohorts and subsections of the population in urban and rural areas are routinely exposed to several environmentally widespread contaminants. Polycyclic aromatic hydrocarbons (PAHs) are a group of over hundred different compounds and have ubiquitous presence in rural and urban environments. Smoke from the combustion of biomass fuel contains a high concentration of carcinogenic PAHs, which are related with several human morbidities. The sources and types of biomass fuel are diverse and wide in distribution. Limited numbers of literature reports have focused the significant impact of PAHs on several components of blood, both in human and wildlife. The toxicity of PAHs to rapidly dividing cells (e.g., bone marrow cells) and other tissues is largely attributed to their reactive oxygenated metabolites, potential of causing oxidative stress, and the adducts of their metabolites with DNA. This review aims to encompass the blood-related effects of PAHs and associated human health risks-an aspect that needs further research-on the population of developing countries of the world in particular.

The present pilot study monitored for the first time volatile organic compounds (VOCs) and aerosols in domestic and occupational microenvironments in the Arctic Region. Differences between the two categories of samples are noted with domestic environments exhibiting higher concentrations of VOCs (total VOCs ranging between 106 and 584 μg m−3), while total particulate matter was highest in workplace non-office environments (ranging between 132 and 284 μg m−3). The terpenes were the most abundant class of VOCs, while a variety of other compounds exhibited 100% frequency of occurrence (i.e. naphthalene, D5-volatile methyl siloxane). Compared to results from other studies/regions, the concentrations of VOCs are considered as relatively low. Based on the results and the knowledge of the typical characteristics of the Arctic lifestyle, some important sources are identified. As this is the first study that deals with indoor air quality in the coldest region globally, it is expected that it will trigger the interest of Authorities to proceed to more detailed studies.

In this study we investigated the clinico-chemical parameters and the level of exposure of brick kiln workers to polycyclic aromatic hydrocarbons (PAHs) in Punjab (Pakistan). The brick kiln workers and a non-occupationally exposed group were recruited for comparative analysis of urinary biomarkers of PAH exposure (i.e. 1-hydroxypyrene (1-OHPyr), α-naphthol and β-naphthol) and blood level of superoxide dismutase (SOD), as a biomarker of oxidative stress and other hematologic parameters. Questionnaires were used to document information on socio-demographic characteristics of all the subjects. The analysis of urinary biomarkers showed higher median concentrations of 1-OHPyr, and α- and β-naphthols in brick kiln workers (1.53, 3.65 and 1.53 μmol/mol-Cr, respectively) than non-occupationally exposed group (0.62, 0.64 and 0.66 μmol/mol-Cr, respectively). The 1-OHPyr in brick kiln workers was above the occupational exposure level. Among the clinical parameters of brick kiln workers, hemoglobin (Hb) and red blood cells (RBCs) were very low and closely associate with 1-OHPyr and β-naphthol. Additionally, the white blood cells (WBCs) and superoxide dismutase (SOD) were also elevated in brick kiln workers, which suggested inflammatory symptoms and high oxidative stress. The results show that regardless of possibly being affected by the poor nutrition, the anemic state and hematological changes observed in brick kiln workers may be associated with their exposure to smoke present in the environment of brick kilns.

Air samples were collected both at an urban and an industrial area of Florence (Italy) in order to evaluate the occurrence, profiles, seasonal variation and gas/particle partitioning of polybrominated diphenyl ethers (PBDEs). The mean total (gas + particle phase) PBDE concentrations were 42.8 ± 7.8 and 89.0 ± 21.1 pg/m^3 in the urban and industrial sites, respectively. In all samples, BDE-209 was the most abundant congener, followed by BDE-47 and BDE-153 in the industrial site, and by BDE-99 in the urban site. The Σ6PBDE (sum of BDE-28, -47, -99, -100, 153, -154) concentrations in the urban (12.1-27.9 pg/m^3) and industrialised (21.4-44.3 pg/m^3) sites were comparable to, or slightly lower than measured at other sites. The partition coefficient of PBDEs between the gas and particle phases (Kp) was well correlated with the subcooled liquid vapor pressure (P°L) for all samples. The measured particulate sorption of PBDEs was compared to the predictions from Junge-Pankow (J/P) model and KOA absorption model. While the Junge-Pankow model tends to overestimate the particulate sorption, the KOA based model seemed to fit the PBDE data.

The levels of dissolved and particle-associated n -alkanes, alkylbenzenes, phthalates, PAHs, anionic surfactants and surfactant fluorescent organic matter (SFOM) were measured in sea-surface microlayer (SML) and sub-surface water (SSL) samples collected in the Leghorn marine environment in September and October 1999. Nine stations, located in the Leghorn harbour and at increasing distances from the Port, were sampled three times on the same day. At all the stations, SML concentrations of the selected organic compounds were significantly higher than SSL values and the enrichment factors (EF=SML concentration/SSL concentration) were greater in the particulate phase than in the dissolved phase. SML concentrations varied greatly among the sampling sites, the highest levels ( n -alkanes 3674 μg/l, phthalates 177 μg/l, total PAHs 226 μg/l) being found in the particulate phase in the Leghorn harbour. To improve the knowledge on pollutant exchanges between sea-surface waters and atmosphere, the validity of spray drop adsorption model (SDAM) was verified for SFOM, surface-active agents, such as phthalates, and compounds which can interact with SFOM, such as n -alkanes and PAHs.

The resolution of two enantiomeric amino acids and four structurally related oxazolidinones was evaluated by reversed-phase planar chromatography using both home-made microcrystalline cellulose triacetate (MCTA) layers and mobile phase additivies, such as beta-cyclodextrins (beta-Cy), modified alpha, beta, gamma cyclodextrins and bovine serum albumin (BSA), on commercially available RP-18W/F254 and SilC18-50/UV254 plates. All the enantiomers were partially or baseline resolved by at least one of the chiral phases tested. Densitograms of optical antipodes and their mixtures were measured on MCTA layers developed with hydroalcoholic solvents.

The direct resolution of nineteen structurally related racemic flavanones was evaluated by reversed-phase planar chromatography using both home-made microcrystalline cellulose triacetate (MCTA) layers and mobile phase modifiers, such as β-cyclodextrin and bovine serum albumin, on commercially available Sil C18-50/UV254 plates. Except for the two glycosides, 5-methoxy-, 7-hydroxy- and 5-hydroxy-7-methoxyflavanone, the enantiomers of other flavanones were all resolved by at least one of the three chiral phases tested. Densitograms of racemic flavanones were measured on MCTA layers developed with alcohol-water mixtures and on Sil C18-50/UV254 plates after elution with chiral mobile phases.

An up-to-date overview of thin-layer chromatography (TLC) techniques for chiral separations of various significant and/or recent examples of enantioresolutions is reported. Furthermore, examples for chiral separations obtained on achiral commercially available C18 TLC plates are described in detail. These include the enantioseparation of methylthiohydantoin-phenylalanine and methylthiohydantoin-tyrosine using hydroxyethyl-β-cyclodextrin as mobile phase additive and the separation of the enantiomers of warfarin and p-chlorowarfarin using bovine serum albumin as mobile phase additive.

An up-to-date overview of thin-layer chromatography (TLC) techniques for chiral separations of various significant and/or recent examples of enantioresolutions is reported. Furthermore, examples for chiral separations obtained on achiral commercially available C18 TLC plates are described in detail. These include the enantioseparation of methylthiohydantoin-phenylalanine and methylthiohydantoin-tyrosine using hydroxyethyl-β-cyclodextrin as mobile phase additive and the separation of the enantiomers of warfarin and p-chlorowarfarin using bovine serum albumin as mobile phase additive.

Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were investigated in eleven edible fish species (5 herbivorous and 6 carnivorous) collected from the River Chenab, Pakistan, during 2007–2009. Total OCP and PCB concentrations (ng g− 1 wet weight, ww) ranged between 13–107 (mean: 38) and 3.1–93.7 (mean: 20) for five herbivorous fish species and 21.6–365 (mean: 148) and 2.5–108 (mean: 30) for six carnivorous species, respectively. The trends of detected organochlorine pesticides (OCPs) in fish samples were: DDTs > PCBs > chlordanes > HCHs. The mean concentration(s) (ng g− 1 ww) of OCPs were relatively higher in all fish species collected near industrial areas followed by urban and agricultural areas. Risk assessment of OCPs and PCBs indicated that fish intake may pose health risk to humans with a consumption rate of > 8 g/person/day. The hazardous ratios for the 50th and 95th percentile data of OCPs and PCBs in fish exceeded the value of 1, suggesting that the daily exposure to OCPs and PCBs yield a lifetime cancer risk greater than 1 in 10,000.

This study evaluates the use of the sandhopper Talitrus saltator as a bioindicator of PAHs contamination of the supralittoral zone of sandy beaches. Adult amphipods were collected at eight localities on the Tuscany shore in summer. Concentrations of 16 PAHs indicated as priority pollutants by the Environmental Protection Agency were determined. T. saltator is able to accumulate PAHs (total PAHs ranging from 0.75 to 62.1 ng g(-1)), with concentrations generally greater than in the sand (total PAHs ranging from 0.04 to 38 ng g(-1)). In particular, it accumulates Phe, Cry, and BbF. Preliminary laboratory tests indicate food as a possible route of PAHs intake by sandhoppers. Despite the need of further studies to clarify the variability of the PAH concentrations found in the substrata and in sandhoppers, T. saltator could be used as a bioindicator of PAHs contamination of the supralittoral zone of sandy shores.

Air samples were collected at different sites in and around two wastewater treatment plants (WWTPs) located in central Italy to determine the concentrations, compositional profiles and contribution to ambient levels of eight polybrominated diphenyl ethers (PBDEs). The investigated WWTPs were selected as they treat industrial wastewater produced by local textile industries along with municipal wastewater. PBDE concentrations within the WWTPs were higher than those measured at reference sites located 4 and 5 km away with BDE-209 dominating the BDE congener composition in all air samples in 2008. Ambient PBDE concentrations measured in and around the WWTPs and estimates of emissions from aeration tanks suggest that WWTPs are sources of PBDEs to ambient air. Principal component analysis and Pearson correlations confirmed this result. The effect of distance from the plant and wind direction on atmospheric concentrations was also investigated. Although the primary fate of PBDEs in WWTPs will be partitioning to sewage sludge, this study suggests that plants can provide a measurable source of these compounds to local ambient air.

Brominated diphenyl ethers (BDE47, 99, 100, and 209) were measured in air, snow and sea ice throughout western Antarctica between 2001 and 2007. BDEs in Antarctic air were predominantly associated with aerosols and were low compared to those in remote regions of the northern hemisphere, except in Marguerite Bay following the fire at Rothera research station in Sept 2001, indicating that this event was a local source of BDE209 to the Antarctic environment. Aerosol BDE47/100 reflects a mixture of commercial pentaBDE products; however, BDE99/100 is suggestive of photodegradation of BDE99 during long-range atmospheric transport (LRAT) in the austral summer. BDEs in snow were lower than predicted based on snow scavenging of aerosols indicating that atmospheric deposition events may be episodic. BDE47, -99, and -100 significantly declined in Antarctic sea ice between 2001 and 2007; however, BDE209 did not decline in Antarctic sea ice over the same time period. Significant losses of BDE99 and -100 from sea ice were recorded over a 19 day period in spring 2001 demonstrating that seasonal ice processes result in the preferential loss of some BDEs. BDE47/100 and BDE99/100 in sea ice samples reflect commercial pentaBDE products, suggesting that photodegradation of BDE99 is minimal during LRAT in the austral winter. funding agencies|National Science Foundation, Office of Polar Programs| 0087872 0741379 |Swedish Research Council||Italian Antarctic Research Program

In previous work [1] hand-made tribenzoylcellulose (CTB) layers developed with ethanol–water and n-hexane–2-propanol mixtures were successfully used for separation of the enantiomers of aromatic alcohols. The alcohols were detected by exposing the plates to iodine vapor for 24 h. This method of visualization does not enable quantitative determination of solutes, because spot intensity quickly decreases as a consequence of iodine vaporization. The intense UV adsorption of the CTB stationary phase, on the other hand, makes it very difficult to detect analytes which adsorb in the same wavelength range. It is, therefore, of great interest to use such chiral plates for the direct resolution and quantitative determination of solutes, e.g. thiochromanol and closely related benzoins, which adsorb strongly at wavelengths where the adsorption of the stationary phase is negligible.

Levoglucosan was present in all samples and its concentrations showed a pronounced annual cycle with maximum levels in the cold season. The annual percentage of ratios of levoglucosan to OC ranged from 0.04 to 9.75% evidencing a major contribution of biomass burning to the aerosol OC during the winter. In the urban-background site, OC was strongly correlated with EC in winter, suggesting that the major fraction of OC was generated as primary particles along with EC. A background levoglucosan component showed that biomass burning was continuously taking place in all the investigated sites. The biomass burning contribution to the Tuscany aerosol was made up of a background component and an additional component during winter probably due to wood burning for domestic heating.

Polycyclic aromatic hydrocarbons (PAHs) associated to PM(2.5) particles were monitored at three sites in the region of Tuscany, Italy, during the period March 2009-March 2010. PAH concentrations ranged between 0.92 ng m(-3) and 13 ng m(-3). The spatial and seasonal differences observed at the three sites are discussed and attributed to specific PAH sources. Benzo[a]Pyrene average annual values were below the EU limit value of 1.0 ng m(-3). The results of this study suggest that emissions from commuting and work related traffic play an important role for the city of Florence, whereas for the city of Livorno, the harbor activities seem to impact the PAH burden substantially, as well. The PAH cancer risk (expressed as the "BaPE index") has shown a 6-fold decline compared to early 1990's concentrations and 2- to 3-fold decline compared to the late 1990's.

Chlorinated and brominated compounds belong to the class of organohalogen compounds that have received attention because of their widespread occurrence, use and applications. Understanding the sources and transformation processes of these contaminants in the environment enables assessment of their possible impact on humans and ecosystems. Recently new and innovative methods of Compound Specific Isotope Analysis have started to be applied to characterize the origin and fate of compounds, their breakdown products and degradation rates in different environmental compartments. Almost all studies have focussed on determination of isotopes of C and H, only recently new methodologies have been developed to measure isotopes of Cl and Br. This review firstly gives a brief description of chemistry properties and geochemical cycle of chlorine and bromine followed by a summary of their uses and applications. In the second section, an overview of CSIA techniques and new challenges and successful applications are also presented.

Polybrominated diphenyl ethers (PBDEs) were determined in sewage sludge samples collected from eight Italian wastewater treatment plants (WWTPs) between June 2009 and March 2010. Total PBDE concentrations ranged from 158.3 to 9427 ng g(-1) dw, while deca-BDE (BDE-209) (concentrations ranging from 130.6 to 9411 ng g(-1) dw) dominated the congener profile in all the samples, contributing between 77% and 99.8% of total PBDE. The suitability of using a magnetic particle enzyme-linked immunoassay (ELISA) to analyse PBDEs in sewage sludge was also tested. The ELISA results, expressed as BDE-47 equivalents, were well correlated with those obtained by GC-NCI-MS, with correlation coefficients (r(2)) of 0.899 and 0.959, depending on the extraction procedure adopted. The risk assessment of PBDEs in sewage sludge addressed to land application was calculated. PEC(soil) values compared to the relative PNEC(soil) for penta and deca-BDE suggests that there is a low risk to the soil environment.

In this study we evaluated the use of Talitrus saltator as biomonitor of polybrominated diphenyl ethers (PBDEs) contamination of the supralittoral zone of Mediterranean sandy shores, an area characterized by a strong input of contaminants but not yet investigated about the presence of these pollutants. We detected the presence of twenty PBDE congeners in amphipods and sand samples collected along the Tyrrhenian coast of central Italy. Eight congeners were detected in all samples. Among them, the BDE-209 was the most abundant in both amphipods and sand samples followed by BDE-99, BDE-153 and BDE-47 in animals, and BDE-99, BDE-47 and BDE-100 in sediment. The ΣPBDEs in amphipods was higher (on the average 2.5-5-fold) than in sand for almost the totality of congeners detected and each sampling site, suggesting the good capacity of sandhoppers to accumulate these pollutants. Moreover statistical analysis revealed significant differences in PBDE concentrations recorded in tissues of T. saltator among sampling sites. Therefore our results suggested the possible utilization of T. saltator as a biomonitor of PBDE contamination of the supralittoral zone of Mediterranean sandy shores.

Pesticides are a group of chemicals made for the purpose of killing or otherwise deterring “pest” species. The word pesticides may refer to insecticides, fungicides, herbicides or other pest control formulations. Introduced in 1940s, organochlorine pesticides (OCPs) were widely used as insecticides in agriculture and pest control until research and public concern regarding the hazards of their use and adverse effects in the environment led to government restrictions and bans. Two International legally binding instruments have been negotiated and concluded: the Protocol to the regional United Nations Economic Commission for Europe Convention on Long Range Transboundary Air Pollution (CLRTAP) on Persistent Organic Pollutants (POPs), opened for signature in June 1998 and entered into force on 23 October 2003 and the Stockholm Convention on POPs, opened for signature in May 2001 and entered into force on 17 May 2004. Both these agreements identify POPs that should be banned and/or phased out or whose use or emissions should be restricted, they include industrial chemicals and by-products such as PCBs, hexachlorobenzene, dioxins and furans, and a number of OCPs such as aldrin, chlordane, DDT, dieldrin, endrin, heptachlor, hexachlorobenzene, mirex and toxaphene. All together are often called the “dirty dozen” (Stockholm Convention, 2004). The hexachlorocyclohexanes (HCHs) are covered by the UNECE Protocol but not the Stockholm Convention. For several listed substances, some limited use is allowed, for example DDT for fighting malaria. Despite the actions of these two Conventions, POPs are still present at high levels in the polar regions and will require vigilant action in the continuing implementation of the Conventions to prevent further contamination of these rich and productive ecosystems. OCPs are organic chemical substances which possess a particular combination of physical and chemical properties and once released into the environment they remain intact for long periods of time (from weeks to decades). They are persistent that is they resist to environmental degradation through chemical, biological and photolytic processes. They are toxic to both humans and wildlife and accumulate in the fatty tissue of living organisms (bioaccumulation), and are found at higher concentrations at higher levels of the food webs (biomagnification). They are subjected to long range transport (LRT) and can be found in remote regions, including Arctic and Antarctica, where they have never been used or produced (i.e.: Su et al., 2006; Bargagli, 2008; Corsolini, 2008; Riget et al., 2010; Donaldson et al., 2010)

In this paper new cellulose tribenzoate/gypsum layers in the ratio up to 8/1 (w/w) were investigated for the chiral resolution of closely related aromatic ketones (e.g. tetralones and indanones), alcohols (e.g. benzhydrols) and racemates or enantiomers of other compound classes (e.g. dinitrophenyl amino acids). Among 22 investigated compounds, 16 racemates were baseline or partially resolved by eluting with methanol or 2-propanol/water mixtures on 4/1 (w/w) layers. The best results were compared with those achieved on microcrystalline cellulose triacetate plates and on cellulose tribenzoate columns. The study of structurally related solutes allowed us to increase the knowledge of the retention and resolution mechanisms on this chiral stationary phase and to highlight the role of π–π interactions between cellulose tribenzoate and solutes with different substituents on the aromatic ring. However, some results were unexpected and confirmed the complexity of enantioseparation mechanisms, thus evidencing the importance of experimental tests. Densitometric scan in the visible region of cellulose tribenzoate/gypsum plates after their exposure to iodine vapours allowed us to successfully perform the quantitative analysis of the investigated compounds, thus overcoming the detection problems normally encountered with this stationary phase.

This paper reports a number of original thin layer chromatography enantioseparations of closely related ketones and alcohols such as tetralones, indanones, and benzhydrols carried out by elution with aqueous-alcoholic mixtures at different ratios. In order to investigate the structural and substituent effects on chiral recognition of microcrystalline cellulose triacetate, the results were compared with those obtained in previous papers for analogous compounds in similar experimental conditions. Even though the inclusion model of retention of analytes on this chiral stationary phase is confirmed, different and unexpected results were obtained for compounds having very favourable characteristics for resolution.

Atlantic bluefin tuna (ABFT) are highly valued and heavily exploited, and critical uncertainties regarding their population structure hinder effective management. Evidence supports the existence of two breeding populations of ABFT; a western population in the Gulf of Mexico and an eastern population in the Mediterranean Sea; both of which migrate and mix in the North Atlantic. Conventional tagging studies suggest low rates of trans-Atlantic migrations; however, electronic tagging and stable isotopes in otoliths indicate stock mixing up to 57% between management zones delineated by 45 degrees W longitude. Here we show that organochlorine pesticides and polychlorinated biphenyls (PCBs) can be used as tracers of bluefin tuna foraging grounds in the North Atlantic and confirm that stock mixing of juvenile tuna within the U.S. Mid Atlantic Bight is indeed high (33-83% eastern origin), and is likely spatially and temporally variable. We further demonstrate that >10% of the Mediterranean population is migratory, that young bluefin tuna migrate from the Mediterranean to western Atlantic foraging grounds as early as age 1, and then return to the Mediterranean Sea as young as age 5, presumably to breed. The tracer method described here provides a novel means for distinguishing bluefin tuna populations and ontogenetic shifts in migration in the North Atlantic.