Flux of Benzo(a)pyrene to the Ground Surface and its Distribution in the Ecosystem

Benzo(a)pyrene (BP) has been investigated in bulk atmospheric deposition, moss, needles of pine and some species of vascular plants. At two remote Lithuanian sites, for 1990-1995 the flux of benzo(a)pyrene from the atmosphere to the ground surface varied between 0.3 to 4.8 μg-2 mo-1. Consequently the territory of Lithuania (65,000 km2) yearly was exposed to 624-2574 kg of carcinogen. The distribution of BP in soil and various vascular plant tissues (Trifolium tepens, Elitrygea repens, Thymus serpyllum) indicates that benzo(a)pyrene is assimilated by flora. The concentration of BP is different in various organs of vascular plants and mostly depends on the degree of soil pollution. More than 300 samples of moss, mostly Hylocomium splendens and Pleurozium schreberi were analyzed for BP. From 3.1 to 896.0 μg kg-1 of BP were measured in the moss samples. The flux of BP to the ground surface correlates well with its concentration in moss. A map of BP flux across Lithuania was created.     

Biological Parameters Towards Polycyclic Aromatic Hydrocarbons Pollution: A Study with Dicentrarchus labrax L. Exposed to the Model Compound Benzo(a)pyrene

The objective of the present study was to investigate the short-term effects of benzo(a)pyrene (BaP) on juvenile sea bass (Dicentrarchus labrax L.) using a multiparameter approach. At the end of the 96?h of exposure to a range of BaP concentrations (2?C256???g?l^?1) in laboratorial conditions, a suite of biomarkers involved in biotransformation pathways, oxidative stress and damage, neurotransmission and energetic metabolism were analysed. Levels of BaP metabolites in bile and BaP-type compounds in tissues were also included as biomarkers of exposure, and the post-exposure swimming velocity was used as a toxicity endpoint at a higher level of biological organisation. In addition, a time-series experiment on the levels of bile BaP metabolites was also performed. Increased levels of BaP metabolites in bile and BaP-type compounds in liver and brain of exposed fish were found, indicating BaP uptake, metabolisation and distribution by different tissues. BaP induced oxidative stress and damage, but no significant effects on the post-exposure swimming velocity, neurotransmission and energetic pathways were found. An increase in the levels of BaP metabolites in bile over time was also observed, reaching a threshold similar at all the concentrations tested. Overall, this integrative multiparameter study reflecting different biological responses of D. labrax was suitable to assess the effects caused by the short-term exposure to BaP and may be useful in the marine environmental risk assessment of polycyclic aromatic hydrocarbons pollution. The observed toxic effects also highlight the relevance of short-term exposure to relatively high concentrations of chemicals, as can occur in the case of punctual heavy chemical releases, such as oil spills in the marine environment.     

Investigating the Uncertainty in Predicting Responses to Atmospheric Deposition using the Model of Acidification of Groundwater in Catchments (MAGIC) within a Generalised Likelihood Uncertainty Estimation (GLUE) Framework

This study investigates the uncertainty associated with the modelled response of a catchment to historic and predicted future acidic deposition for the period 1851–2041. The MAGICmodel is applied within a GLUE framework to the 3.88 km² Afon Gwy catchment at Plynlimon, Wales. Nine million Monte Carlo simulations resulted in 5700 being accepted as behaviouralas defined by a fuzzy measure comparing observed to simulated variables. Model output and parameter sensitivity analysis indicate that, for this example where weathering rates are low,model dynamics are limited compared to control exerted by modelinitial conditions and by the specified acidic deposition boundary conditions. The results show that despite the small number of behavioural simulations, they are widely spread acrossthe ranges for most of the parameters varied. The GLUE methodology allows simulated prediction ranges for important variables to be presented as quantitative likelihood weighteduncertainty estimates rather than a single prediction for eachvariable over time.     

Addition of porphyrins to cigarette filters to reduce the levels of benzo[a]pyrene (B[a]P) and tobacco-specific N-nitrosamines (TSNAs) in mainstream cigarette smoke

Tobacco-specific N-nitrosamines (TSNAs) and benzo[a]pyrene (B[a]P) in mainstream cigarette smoke (MSS) cause smoking-related diseases and environmental pollution. Porphyrins were added to cigarette filters to reduce B[a]P (porphyrins A-E) and TSNAs (porphyrin F) in MSS. The porphyrin-B[a]P and porphyrin F-TSNAs (N'-nitrosoanabasine (NAB), N'-nitrosoanatabine (NAT), 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), and N-nitrosonornicotine (NNN)) interactions were investigated by fluorescence quenching and UV-visible spectroscopy. The correlation coefficients were 0.987-0.997 (B[a]P) and 0.994-0.999 (TSNAs), and the binding constants were (1.67-5.02) × 10(5) (B[a]P) and 3.42 × 10(3)-1.40 × 10(4) (TSNAs). Up to 36.72% of B[a]P and 46.67% of the TSNAs were eliminated from MSS, with greater reductions when more porphyrin was included in the filter. With the same mass of porphyrin in the filter, the reduction trend for B[a]P by porphyrins A-E was A > B > C > D > E. The reduction trend for TSNAs by porphyrin F was NNN > NAB > NNK > NAT. The porphyrin mode of action is possibly through strong π-π interactions.     

Long-Term Soil Acidification Model (LTSAM) Development and Application for Analyzing Soil Responses to Acidic Deposition

A long-term soil acidification model (LTSAM) which can describe calcareous and non-calcareous soil responses to acidic deposition is developed based on the conservation of alkalinity and Ulrich buffer ranges. The model which considers nine major ions of armospheric deposition, has focused on certain soil processes (weathering of carbonates, silicates, and aluminum (Al) oxides or hydroxides, cation exchange, anion retention, and CO2 solubility). After comparing the model design and simulation results with the SMART, the paper describes several numerical experiments on the sensitivity of calcareous drab soil in Beijing and red earth (nearly dystric cambisol) in Wenzhou of Zhejiang Province in Southern China to acidic deposition scenarios. The modelling results indicate that increase or decrease in atmospheric deposition of base cations and not only changes in deposition of sulfate (S) and H+ must be considered in assessment of critical loads both for red earth and calcareous drab soil.     

Predicting Recovery from Acidic Deposition: Applying a Modified TAF (Tracking and Analysis Framework) Model to Maine (USA) High Elevation Lakes

We adapted a reduced-form model, built to predict the aquatic effects of alternative nitrogen and sulfur emissions scenarios on Adirondack lakes, New York, for use on high elevation lakes of Maine (HELM), USA. The Tracking and Analysis Framework (TAF) model was originally designed to evaluate the biotic, economic, and health effects of acid deposition. The TAF model developed in our study was used to assess the biotic effects of different levels of sulfate deposition resulting from alternative emissions scenarios. The aquatic portion of the model is based on a lumped-parameter watershed chemistry model, MAGIC (Model of Acidification of Groundwater in Catchments). The original TAF model was built by calibrating MAGIC to 33 lakes in the Adirondack Mountains. We calibrated MAGIC to 78 HELM lakes, and built reduced-form models from these MAGIC predictions. We evaluated TAF predictions of acid neutralizing capacity (ANC), a fish acid stress index (ASI), and the probability of fish presence in 2030 for four different SO₂ emissions-reduction scenarios. The most dramatic emissions reduction scenario produced only modest increases in mean ANC (16.8 μeq/L ± 7.9 μeq/L) and slight increases in mean predicted probability of presence of acid-sensitive fish (0.07± 0.09) across all lakes. However, a small number of lakes were predicted to have more substantial increases in ANC and improvements in other conditions for acid-sensitive fish. Our results reflect the reality that many of the high elevation lakes of Maine historically had low ANC and that some were even acidic in pre-industrial times. Thus, ’recovery’ for most of the high elevation lakes of Maine will be modest under any scenario of reduced acidic deposition.     

Application of a molecular sensory science approach to alkalized cocoa (Theobroma cacao): structure determination and sensory activity of nonenzymatically C-glycosylated flavan-3-ols

Application of comparative taste dilution analyses on nonalkalized and alkalized cocoa powder revealed the detection of a velvety, smoothly astringent tasting fraction, which was predominantly present in the alkalized sample. LC-MS/MS analysis, 1D- and 2D-NMR, and CD spectroscopy as well as model alkalization reactions led to the unequivocal identification of the velvety, smoothly astringent molecules as a series of catechin- and epicatechin-C-glycopyranosides. Besides the previously reported (-)-epicatechin-8-C-beta-D-galactopyranoside, additional flavan-3-ol-C-glycosides, namely, (-)-epicatechin-8-C-beta-D-glucopyranoside, (-)-catechin-8-C-beta-D-glucopyranoside, (-)-catechin-6-C-beta-D-glucopyranoside, (-)-epicatechin-6-C-beta-D-glucopyranoside, (-)-catechin-8-C-beta-D-galactopyranoside, (-)-catechin-6-C-beta-D-galactopyranoside, (-)-catechin-6-C,8-C-beta-D-diglucopyranoside, (-)-epicatechin-6-C,8-C-beta-D-digalactopyranoside, (-)-catechin-6-C,8-C-beta-D-digalactopyranoside, and epicatechin-6-C,8-C-beta-D-diglucopyranoside, were identified for the first time in cocoa. Most surprisingly, these phenol glycoconjugates were demonstrated by model experiments to be formed via a novel nonenzymatic C-glycosylation of flavan-3-ols. Using the recently developed half-tongue test, human recognition thresholds for the astringent and mouth-drying oral sensation were determined to be between 1.1 and 99.5 micro mol/L (water) depending on the sugar and the intramolecular binding position as well as the aglycone.     

Electrochemical Production of Ferrate (Iron VI): Application to the Wastewater Treatment on a Laboratory Scale and Comparison with Iron (III) Coagulant

This paper presents a comparative study of the performance of ferrate(VI), FeO ₄ ^2? , and ferric, Fe(III), towards wastewater treatment. The ferrate(VI) was produced by electrochemical synthesis, using steel electrodes in a 16 M NaOH solution. Domestic wastewater collected from Hailsham North Wastewater Treatment Works was treated with ferrate(VI) and ferric sulphate (Fe(III)). Samples were analysed for suspended solids, chemical oxygen demand (COD), biochemical oxygen demand (BOD) and P removal. Results for low doses of Fe(VI) were validated via a reproducibility study. Removal of phosphorous reached 40% with a Fe(VI) dose as low as 0.01 mg/L compared to 25% removal with 10 mg/L of Fe(III). For lower doses (<1 mg/L as Fe), Fe(VI) can achieve between 60% and 80% removals of SS and COD, but Fe(III) performed even not as well as the control sample where no iron chemical was dosed. The ferrate solution was found to be stable for a maximum of 50 min, beyond which Fe(VI) is reduced to less oxidant species. This provided the maximum allowed storage time of the electrochemically produced ferrate(VI) solution. Results demonstrated that low addition of ferrate(VI) leads to good removal of P, BOD, COD and suspended solids from wastewater compared to ferric addition and further studies could bring an optimisation of the dosage and treatment.     

Determination and Evaluation of Sampling Velocity in a Simple Passive Sampling Method to Monitor HNO3(g) in Ambient Air

We evaluated the applicability of a simple passive sampling method to quantify HNO₃(g) in ambient air. The method has the advantages of not only ease of operation but also low cost. A sampling velocity of 214 m day^?1 was determined based on the concentration of HNO₃(g) measured by the four-stage filter-pack method at nine sites located within a 250?×?250-km area in Japan. This sampling velocity was applied at sites located outside of area to verify the applicability and accuracy of the simple passive sampling method. The variation in the results for the application of the sampling velocity ranged from 0.39 to 0.95. The simple passive sampling method should be applied to sites with different meteorological conditions, and the obtained data should be used to obtain more significant information and/or to indicate the need for further developments in the methodology.     

Application of the 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation assay to a flow injection system for the evaluation of antioxidant activity of some pure compounds and beverages

The 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation (ABTS(*)(+)) assay was adapted to a flow injection (FI) system to obtain a sensitive and rapid technique for the monitoring of antioxidant activity of pure compounds and complex matrixes, such as beverages and food extracts. The FI system includes a HPLC pump that flows the mobile phase (a solution of ABTS(*)(+) in ethanol) through a 20 microL loop injector, a single bead string reactor filled with acid-washed silanized beads, a delay coil and a photodiode array UV-visible detector. The technique was very sensitive, with limits of detection and of quantification of 4.14 and 9.29 micromol of Trolox/L, respectively, and demonstrated high repeatability and reproducibility. The proposed technique was then applied to the evaluation of the antioxidant activity of some pure compounds, demonstrating good agreement with published data obtained by the original spectrophotometric ABTS(*)(+) assay. Finally, the total antioxidant activity of 10 beverages was determined by both the proposed and the original method. The values ranged from 0.09 mmol L(-)(1) for cola to 49.24 mmol L(-)(1) for espresso coffee and did not result significantly different from those obtained by the original spectrophotometric ABTS(*)(+) assay (Student's paired t-test: t = 1.4074, p = 0.1929). In conclusion, the proposed FI technique seems suitable for the direct, rapid and reliable monitoring of total antioxidant activity of pure compounds and beverages and, due to the ability to operate in continuous, it allows the analysis of about 30 samples h(-)(1) making the assay particularly suitable for large screening of total antioxidant activity in food samples.     

The Influence of Soil Properties on the Water Pollution (Nitrate,Phosphate and COD) Following a Single Application of Sewage Sludge to 70 Contrasting Agricultural Soils

The aim was to study the influence of soil properties on the leaching of nitrate, phosphate and organic matter (OM) following the application of sewage sludge to contrasting soils. Seventy agricultural soils from different parts of Spain were amended with sewage sludge (50 t dry weight ha⁻¹), and a controlled column study was developed. After 2, 4 and 6 months of incubation, distilled water, equivalent to an autumn rainfall event of 25 l m⁻² in Mediterranean environments, was applied and leachates collected and analysed: pH, electrical conductivity (EC), chemical oxygen demand (COD), phosphate and nitrate. The mean values of pH in the leachates after 2, 4 and 6 months were similar and close to the neutrality. The highest concentrations for the rest of the parameters analysed were found after 2 months of incubation and diminished for 4 and 6 months, especially COD. Soil pH and texture were the most relevant soil properties controlling the leaching of the analysed parameters. The OM mineralization seemed to be enhanced at high values of soil pH, thus increasing the nitrate and reducing the COD leaching. However, phosphate levels were reduced at high values of soil pH. In addition, leaching was promoted in sandy soils. Other soil properties influenced phosphate leaching being the equivalent calcium carbonate soil content as the most relevant. Soil organic carbon was negatively related to the EC and nitrate concentration in the leachates but resulting in a weak contribution compared with soil pH and texture. Concerns about nitrate pollution have been confirmed.