QSPR for prediction of subcooled vapor pressures (log PL) of polychlorinated trans-azobenzenes

In this study the values of subcooled vapor pressures (log P(L)) were estimated for 209 trans chloroazobenzenes (Ct-ABs) that fill some gaps in analytical and experimental data on these compounds. There are 209 chloro derivatives of trans azobenzenes that are relatively stable and more environmentally relevant than 209 chloro cis congeners. The calculations models were based on the Quantitative Structure-Property Relationship (QSPR) scheme using the semi-empirical method (PM6) in molecular package (MOPAC) software and density functional theory (DFT) method using B3LYP functional and 6-311++G** basis set) in Gaussian 03 software method and the artificial neural networks (ANNs) prediction. The values of log P(L) predicted by models used varied between -3.94 to -2.66 for Mono-; -4.85 to -2.97 for Di-; -5.18 to -3.17 for Tri-; -6.02 to -3.77 for Tetra-; -6.64 to -4.64 for Penta-; -7.36 to -4.76 for Hexa-; -7.54 to -5.79 for Hepta-; -7.75 to -6.64 for Octa-; -7.89 to -7.44 for Nona-Ct-Abs; and -8.09 and -8.13 for Deca-Ct-AB. Based on these values Ct-ABs can be grouped localized among relatively low (log P(L) -4 to -2) and low (log P(L) < -4) mobile Persistent Organic Pollutants (POPs). Both the calculation methods employed were characterized by similar prediction ability of subcooled vapor pressure values of Ct-ABs, while those of PM6 are much more efficient due to a cheaper hardware used and around 300-fold less time spent on calculations.     

Novel insights in Al-MCM-41 precursor as adsorbent for regulated haloacetic acids and nitrate from water

High concentration of NO ₃ ^? in groundwater has raised concern over possible contamination of drinking water supplies. In addition, the formation of haloacetic acids (HAAs) as by-products during disinfection with chlorine-based agents is still a relevant issue, since HAAs pose serious health hazard. In this work, we investigated the affinity of a precursor of Al-MCM-41 (a mesostructured hexagonal aluminosilicate containing the template surfactant) towards nitrate and HAAs, for its possible application in the removal of these pollutants from natural and drinking waters. Additionally, adsorption kinetics and isotherms were studied. The adsorbent was synthesized using cetyltrimethylammonium bromide as surfactant and characterized by physico?Cchemical techniques. Simulated drinking water was spiked with the EPA-regulated HAAs (monochloroacetic (MCAA), monobromoacetic (MBAA), dichloroacetic (DCAA), dibromoacetic (DBAA), and trichloroacetic (TCAA) acids) and placed in contact with the adsorbent. The effect of matrix composition was studied. Adsorption kinetic studies were performed testing three kinetics models. For the adsorption studies, three adsorption isotherm approaches have been tested to experimental data. The pollutant recoveries were evaluated by suppressed ion chromatography. The affinity of the adsorbent was TCAA = DBAA = DCAA > MBAA > MCAA with DCAA, DBAA, and TCAA completely removed. A removal as high as 77?% was achieved for 13?mg/L nitrate. The adsorption isotherms of NO ₃ ^? and monochloroacetic acid can be modeled by the Freundlich equation, while their adsorption kinetics follow a pseudo-second-order rate mechanism. The adsorbent exhibited high affinity towards HAAs in simulated drinking water even at relevant matrix concentrations, suggesting its potential application for water remediation technologies.     

Marine macrophytes as effective lead biosorbents

Several species of seagrass and marine macrophytes were investigated for their biosorption performance in the removal of lead from aqueous solution. The effect of pH on the equilibrium of the seagrass Cymodocea nodosa as a biosorbent also was studied. It was found that increasing pH increased lead biosorption, with a maximum uptake of approximately 140 mg/g in the range pH 3.3 to 5. Equilibrium data at different pH levels were successfully fitted to competitive equilibrium models. In addition, the seaweeds belonging to different phyla (i.e., Chlorophyta, Heterokontophyta, and Rhodophyta) were studied for the effect of their structure on equilibrium at a constant pH 5. The brown algae (Heterokontophyta) showed the highest potential for lead sorption, with a maximum uptake of 220 mg/g for C. compressa and 140 mg/g for S. lomentaria. The green algae (Chlorophyta) showed lead uptake in the range 40 to 90 mg/g, and the red algae (Rhodophyta) was least effective, with uptake in the range 10 to 40 mg/g.     

Imidacloprid movement in soils and impacts on soil microarthropods in southern Appalachian eastern hemlock stands

Imidacloprid is a systemic insecticide effective in controlling the exotic pest (hemlock woolly adelgid) in eastern hemlock () trees. Concerns over imidacloprid impacts on nontarget species have limited its application in southern Appalachian ecosystems. We quantified the movement and adsorption of imidacloprid in forest soils after soil injection in two sites at Coweeta Hydrologic Laboratory in western North Carolina. Soils differed in profile depth, total carbon and nitrogen content, and effective cation exchange capacity. We injected imidacloprid 5 cm into mineral soil, 1.5 m from infested trees, using a Kioritz soil injector. We tracked the horizontal and vertical movement of imidacloprid by collecting soil solution and soil samples at 1 m, 2 m, and at the drip line from each tree periodically for 1 yr. Soil solution was collected 20 cm below the surface and just above the saprolite, and acetonitrile-extractable imidacloprid was determined through the profile. Soil solution and extractable imidacloprid concentrations were determined by high-performance liquid chromatography. Soil solution and extractable imidacloprid concentrations were greater in the site with greater soil organic matter. Imidacloprid moved vertically and horizontally in both sites; concentrations generally declined downward in the soil profile, but preferential flow paths allowed rapid vertical movement. Horizontal movement was limited, and imidacloprid did not move to the tree drip line. We found a negative relationship between adsorbed imidacloprid concentrations and soil microarthropod populations largely in the low-organic-matter site; however, population counts were similar to other studies at Coweeta.     

Fish pollution with anthropogenic 137Cs in the southern Baltic Sea

This paper presents the results of a study on changes in ¹³⁷Cs activity concentrations in three fish species from the southern Baltic Sea: cod (Gadus morhua), herring (Clupea harengus) and flounder (Platichtys flesus), in the period 2000–2010. During the study period a marked decline in cesium activity concentration in fish muscle tissue was observed, which reflected changes in radionuclide activity concentration in seawater. No statistically significant temporal trends were determined in changes of concentration factors (CF_{fish/seawater}) calculated for the examined fish species. The analysis of ¹³⁷Cs activity as a function of ichthyological parameters revealed the lack of a relationship between radionuclide activity concentrations in herring muscle tissue and the fish age in an narrow age range (2–4 years). However, a reverse proportionality of total fish mass, as well as body length, against ¹³⁷Cs activity concentrations in muscles was well documented. The latter observation can be the direct result of the dilution effect related to the increase of fish body weight. ¹³⁷Cs activity concentration in muscle tissue of the five fish species forms a declining sequence: Gadus morhua, Platichthys flesus, Clupea harengus, Perca fluviatilis and Neogobius melanostomus.     

Styrofoam debris as a potential carrier of mercury within ecosystems

The present paper falls within the trend of research into interactions between various pollutants emitted anthropogenically into the environment and focuses on mercury and styrofoam debris. The study covers part of the Southern Baltic’s drainage area. Apart from styrofoam and beach sand, the research involved mosses, which are bioindicators of atmospheric metal pollution. The research has shown that mercury present in the environment becomes associated with styrofoam debris. The median for mercury concentrations in virgin styrofoam samples (0.23 ng g^?1 dry weight (d.w.)) and in beach sand samples (0.69 ng g^?1 d.w.) was an order of magnitude lower than in the styrofoam debris (5.20 ng g^?1 d.w.). The highest mercury content observed in styrofoam debris (3,863 ng g^?1 d.w.) exceeded the standards for bottom sediment and soil. The binding of mercury to styrofoam debris takes place in water, and presumably also through contact with the ground. A significant role in this process was played by biotic factors, such as the presence of biofilm and abiotic ones, such as solar radiation and the transformations of mercury forms related to it. As a result, mercury content in styrofoam debris underwent seasonal changes, peaking in summertime. Furthermore, the regional changes of mercury content in the studied debris seem to reflect the pollution levels of the environment.     

Tributyltin (TBT) induces oxidative stress and modifies lipid profile in the filamentous fungus Cunninghamella elegans

To investigate the response of the tributyltin-degrading fungal strain Cunninghamella elegans to the organotin, a comparative lipidomics strategy was employed using an LC/MS-MS technique. A total of 49 lipid species were identified. Individual phospholipids were then quantified using a multiple reaction monitoring method. Tributyltin (TBT) caused a decline in the amounts of many molecular species of phosphatidylethanolamine or phosphatidylserine and an increase in the levels of phosphatidic acid, phosphatidylinositol and phosphatidylcholine. In the presence of TBT, it was observed that overall unsaturation was lower than in the control. Lipidome data were analyzed using principal component analysis, which confirmed the compositional changes in membrane lipids in response to TBT. Additionally, treatment of fungal biomass with butyltin led to a significant increase in lipid peroxidation. It is suggested that modification of the phospholipids profile and lipids peroxidation may reflect damage to mycelium caused by TBT.     

Mercury in certain boletus mushrooms from Poland and Belarus

This paper reports the results of the study of Hg contents of four species of Boletus mushroom (Boletus reticulatus Schaeff. 1763, B. pinophilus Pilát & Dermek 1973, B. impolitus Fr. 1838 and B. luridus Schaeff. 1774) and the surface soils (0–10 cm layer, ～100 g) samples beneath the mushrooms from ten forested areas in Poland and Belarus by cold-vapour atomic absorption spectroscopy. The ability of the species to bioconcentrate Hg was calculated (as the BCF) while Hg intakes from consumption of these mushroom species were also estimated. The median Hg content of the caps of the species varied between 0.38 and 4.7 mg kg^?1 dm; in stipes between 0.13 and 2.5 mg kg^?1 dm and in the mean Hg contents of soils varied from 0.020 ± 0.01 mg kg^?1 dm to 0.17 ± 0.10 mg kg^?1 dm which is considered as “background” Hg level. The median Hg content of caps of B. reticulatus and B. pinophilus were up to 4.7 and 3.6 mg kg^?1 dm, respectively, and they very efficiently bioaccumulate Hg with median BCF values of up to 130 for caps and 58 for stipes. The caps and stipes of these mushrooms if eaten will expose consumer to elevated dose of total Hg estimated at 1.4 mg for caps of Boletus reticulatus from the Kacze ??gi site, which is a nature reserve area. Nevertheless, the occasional consumption of the valued B. reticulatus and B. pinophilus mushrooms maybe safe.     

Annual Average Radon Concentrations in California Residences

A study was conducted to determine the annual average radon concentrations in California residences, to determine the approximate fraction of the California population regularly exposed to radon concentrations of 4 pCI/l or greater, and to the extent possible, to identify regions of differing risk for high radon concentrations within the state. Annual average indoor radon concentrations were measured with passive (alpha track) samplers sent by mail and deployed by home occupants, who also completed questionnaires on building and occupant characteristics. For the 310 residences surveyed, concentrations ranged from 0.10 to 16 pCI/l, with a geometric mean of whole-house (bedroom and living room) average concentrations of 0.85 pCI/l and a geometric standard deviation of 1.91. A total of 88,000 California residences (0.8 percent) were estimated to have radon concentrations exceeding 4 pCI/l. When the state was divided into six zones based on geology, significant differences in geometric mean radon concentrations were found between several of the zones. Zones with high geometric means were the Sierra Nevada mountains, the valleys east of the Sierra Nevada, the central valley (especially the southern portion), and Ventura and Santa Barbara Counties. Zones with low geometric means included most coastal counties and the portion of the state from Los Angeles and San Bernardino Counties south.     

The Use of Stable Isotopes to Differentiate Specific Source Markers for MTBE

The recent controversy over the use of MTBE within gasoline to boost oxygen content and decrease carbon monoxide emissions to the atmosphere has led to a proposed phase-out of this compound by 2002. This paper is a preliminary investigation into the use of gas chromatography isotope-ratio mass spectrometry (GCIRMS) to determine both carbon and hydrogen isotopic compositions of MTBE as a means of differentiating sources of MTBE. Three pure MTBE samples were purchased from chemical distributors. Little variation of the i 13 C values were observed although the samples had isotopically distinct i -D values. Four different methods of obtaining carbon isotope ratios of neat MTBE, MTBE in gasoline, and MTBE in water are described, and the precision and accuracy of each is discussed. The carbon isotopic compositions of MTBE within 10 gasoline samples from three different areas of the United States show a wide range of carbon isotope compositions. This novel method of MTBE analysis could be valuable in forensic investigations.