Distribution and transport of coal tar-derived PAHs in fine-grained residuum

We investigated the distribution and transport of coal tar-derived polycyclic aromatic hydrocarbons (PAHs) in fine-grained residuum and alluvial floodplain deposits that underlie a former manufactured gas plant. All 16 USEPA priority pollutant PAHs are present at this site and have penetrated the entire 4-5m thickness of clayey sediments, which unconformably overly limestone bedrock. Concentrations of less hydrophobic PAHs (e.g., naphthalene, 0.011-384mg kg(-1)) were about 10 times higher than those of highly hydrophobic PAHs (e.g., benzo[g,h,i]perylene -0.002 to 56.03mgkg(-1)). Microscopic examination of thin-sections of the clay-rich sediments showed that fractures and rootholes, which can act as pathways for flow, occur throughout the profiles. Tarry residue was found coating some fractures and rootholes, indicating that coal tar was, in some cases, able to penetrate as an immiscible phase. However, in the vast majority of samples in which PAHs were detected, there was no detectable tar residue, suggesting that much of the transport occurred in the dissolved phase. Examination of thin-sections with an epifluorescent microscope indicated that PAHs, which fluoresce brightly when exposed to UV light, are distributed throughout the soil matrix, rather than being confined to fractures and rootholes. The widespread distribution of PAHs is most likely due to diffusion-controlled exchange between the fast-flow pathways in the fractures and rootholes and the relatively immobile water in the fine-grained matrix. This implies that fractures and rootholes can play a major role in controlling transport of highly hydrophobic compounds in fine-grained sediments, which would otherwise act as barriers to contaminant migration.     

Optimisation of pressurised liquid extraction for elimination of sulphur interferences during determination of organotin compounds in sulphur-rich sediments by gas chromatography with flame photometric detection

A simple method for species-selective analysis of organotin compounds (OTCs) (butyl and phenyl) in sediments was developed. The sample preparation procedure was specifically optimised for sulphur-rich sediments to eliminate interferences from elemental sulphur and organosulphur compounds. Tin species were extracted from sediment samples using pressurised liquid extraction technique (PLE), ethylated - with simultaneous extraction to isooctane - in aqueous phase with sodium tetraethylborate (NaBEt(4)) and separated/detected by gas chromatography with flame photometric detection (GC-FPD). PLE operational variables (extraction temperature and pressure, solvent composition and number of static extraction steps) and extract handling routine were fine-tuned to minimise the amount of extracted interferents while keeping OTCs recovery at an acceptable level. Best results were obtained after extraction of sediment samples with methanol/water (75% v/v methanol) solution of acetic acid/sodium acetate with tropolone addition (0.6 g l(-1)). Derivatisation of low temperature, high-pressure (50 degrees C, 13.8 MPa) extracts gives isooctane extracts which are clean enough to be directly analysed by GC-FPD without any further cleanup. Interferences from elemental sulphur were completely eliminated while concentrations of other interferents were reduced to the level not impairing quantitation of OTCs under the study. No negative effects in terms of chromatographic column deterioration were observed after repeated injections of such extracts. Two certified reference materials, BCR646 and PACS-2, were analysed to assess performance of the method. Recoveries of all OTCs under the study, except MBT, were in the range of 91-114%. MBT extraction efficiency was low (34-47%) therefore the method is unsuitable for precise determinations of this compound.     

Heavy metal-rich wastes sequester in mineral phases through a glass-ceramic process

Certain sludges generated by industry are rich in contaminating elements and are a major environmental problem. In this study, we determine the ability of these contaminating elements to be incorporated into a glass-matrix and in various mineral phases after a crystallization process. The contaminating elements studied were obtained from sewage sludges (SS) and galvanic sludges (GS), our raw materials. The sludge samples were taken from urban wastewater treatment plant in Catalonia (NE Spain) with high levels of phosphorus oxide (P(2)O(5)). In silica glasses, P(2)O(5) acts as a network former. We determined the chemical composition of both the SS and GS, as well as their thermal behaviour by differential thermal analysis and thermal gravimetric analysis (DTA-TG) to obtain their melting curves. The vitreous transition temperature of the obtained glass was established by dilatometer technique at 725 degrees C. The DTA-TG curve of the glass obtained has an exothermal wide peak at 860 degrees C corresponding to crystallization of the two phases: a spinel phase and a phosphate phase. A second exothermal wide peak at 960 degrees C was attributed to the crystallization of aluminium pyroxene, anorthite and fluor-apatite, with two exothermal phenomena attributed to the evolution of these phases. An exothermal peak at 1100 degrees C was attributed to gehlenite crystallization. Scanning electron microscope observations and energy-dispersed X-ray spectroscopy microanalyses of glass-ceramic showed that the contaminating elements were concentrated in the spinel phases, which are the first phases to crystallize during the cooling of glass. Finally, the spinel structure permits the incorporation of all the contaminating elements into it.     

Promoting the O3 flux concept for European forest trees

Tropospheric ozone (O3) levels are predicted to stay high, being a factor within "global change" with potential effects on the carbon sink strength of forest trees. Hence, new approaches to O3 risk assessment and their validation are required, although appropriate databases for adult trees are scant. Approaches based on external O3 exposure are presently being evaluated against the ones on O3 flux into leaves, as the cumulative uptake has the capacity for deriving O3 risk from cause-effect relationships. The effective dose, however, needs to account for the trees' O3 defence and tolerance in addition to O3 uptake. The current status of promoting the preferable mechanistic O3 flux concept is highlighted for major regions of Europe, addressing refinements and simplifications needed for routine use. At the pan-European scale, however, the flux-based concept is ready for use in O3 risk assessment and has the potential of meso-scale application at the forest ecosystem level.     

Effect of pre-treatment and supporting media on Ni(II), Cu(II), Al(III) and Fe(III) sorption by plant root material

In this work Paspalum notatum root material was used to elucidate the influence of acid leaching pre-treatment and of sorption medium on metal adsorption. Ground P. notatum root was leached with 0.14M HNO(3). Leached root material (LRM) and non-leached root material (NLRM) were employed to flow sorption of Ni(II), Cu(II), Al(III) and Fe(III) in 0.5M CH(3)COONH(4) medium at pH 6.5. For LRM the sorption was also studied in 0.5M KNO(3) medium. The acid pre-treatment increased the sorption capacity (SC) for all ions studied. For the KNO(3) medium, Cu(II) and Fe(III) sorption was higher than in CH(3)COONH(4) and the type of the Ni(II) isotherm's model changed. The Freundlich model was the most representative isotherm model to describe metallic ions sorption. The (1)H NMR spectra showed differences between LRM and NLRM and the acid-basic potentiometric titration elucidated that acid-leaching procedure affected the root material sorption sites once only two predominant sorption sites were found for LRM (phenolic and amine, both able cations sorption) and five sorption sites (two carboxylic, amine and two phenolic) were founded for NLRM.     

Geochemical fractions of copper in soil chronosequences of selected European floodplains

The influence of soil formation on copper sorption is documented based on chronosequences of soils from three river floodplains in Europe (Danube, Ebro and Elbe). Sequential extraction was used to fractionate copper in original and spiked soils in order to study the long-term and short-term behaviour of copper retention. Copper partitioning among defined geochemical fractions was mainly determined by soil pH and the contents of carbonates, organic matter and Fe-/Mn-oxides and hydroxides. Copper extracted with NH(2)OH.HCl correlated well with the contents of crystalline Fe-oxides and hydroxides, demonstrating increasing retention capacity with progressing soil development. Copper retained in original soils was found in more strongly bound fractions, whereas sorption of freshly added copper was primarily influenced by the presence of carbonates. Beyond the effect of progressing soil formation, variations in organic carbon contents due to different land use history affected the copper retention capacity of the investigated soils.     

Kinetic and adsorption study of acid dye removal using activated carbon

The adsorption of three acid dyes, Acid Red 97, Acid Orange 61 and Acid Brown 425 onto activated carbon was studied for the removal of acid dyes from aqueous solutions at room temperature (25 degrees C). The adsorption of each dye with respect to contact time was then measured to provide information about the adsorption characteristics of activated carbon. The rates of adsorption were found to conform to the pseudo-second-order kinetics with a good correlation. The experimental isotherms obtained, except for Acid Orange 61 studied in mixture, were of the S-type in terms of the classification of Giles and co-workers. The best fit of the adsorption isotherm data was obtained using the Freundlich model. When a comparative study was made of the results obtained with single and mixed dyes, it can be seen that some of them affect others and modify their behavior in the adsorption process. The results indicate that activated carbon could be employed for the removal of dyes from wastewater.     

Acetylcholinesterase-polyaniline biosensor investigation of organophosphate pesticides in selected organic solvents

The behavior of an amperometric organic-phase biosensor consisting of a gold electrode modified first with a mercaptobenzothiazole self-assembled monolayer, followed by electropolymerization of polyaniline in which acetylcholinesterase as enzyme was immobilized, has been developed and evaluated for organophosphorous pesticide detection. The voltammetric results have shown that the formal potential shifts anodically as the Au/MBT/PANI/AChE/PVAc thick-film biosensor responded to acetylthiocholine substrate addition under anaerobic conditions in selected organic solvent media containing 2% v/v 0.05 M phosphate buffer, 0.1 M KCl (pH 7.2) solution. Detection limits in the order of 0.147 ppb for diazinon and 0.172 ppb for fenthion in acetone-saline phosphate buffer solution, and 0.180 ppb for diazinon and 0.194 ppb for fenthion in ethanol-saline phosphate buffer solution has been achieved.     

Fluorescence fingerprints and Cu2+-complexing ability of individual molecular size fractions in soil- and waste-borne DOM

Land spreading of organic materials introduces large amounts of dissolved organic matter (DOM) into the soil. DOM has the ability to form stable complexes with heavy metals and can facilitate their transport towards the groundwater. The effects on soil processes are difficult to assess, because different DOM components might react differently towards metal ions. The objective of this study was to investigate the fluorescence signature and the Cu2+-binding capacity of individual molecular size fractions of DOM from various sources. DOM extracted from leaf compost, chicken manure, sugar cane vinasse and a fulvic hypercalcaric cambisol was fractionated by the means of dialysis into four molecular size classes: MW<500, 50012000-14000 Da. Vinasse and leaf compost contained around 80% and 70%, respectively, of the total organic carbon in the fractions with low molecular weight (MW<3500 Da); in chicken manure and soil these fractions accounted for 40% and 50% only. Fluorescence was highest in the fraction MW>12000 Da for leaf compost, chicken manure and soil. The opposite result was obtained for vinasse, where the fractions with low molecular weight showed highest fluorescence intensities, distinguishing it from all other samples. Vinasse showed the greatest ability to bind Cu2+ with a resulting complex concentration of 6.31mgl(-1) while in contact with an excess of Cu2+. Leaf compost, soil and chicken manure followed with 2.69, 1.12, and 0.85mgl(-1), respectively. Within vinasse, the fraction MW<500 Da was able to form the most DOM-Cu complexes, indicating the importance of low molecular weight fractions in metal binding.     

Spatial and temporal variations and possible sources of dichlorodiphenyltrichloroethane (DDT) and its metabolites in rivers in Tianjin, China

Water, suspended solid (SS) and sediment samples were collected from nine water courses in Tianjin, China and analyzed for dichlorodiphenyltrichloroethane (DDT) and its metabolites (DDXs, including o,p'-,p,p'-DDT, DDD and DDE). The average DDX concentrations in water, SS and sediment were 59+/-30 ng l(-1), 2690+/-1940 ng g(-1)dry wt. and 340+/-930 ng g(-1)dry wt., respectively. Due to the termination of the extensive agricultural application and industrial manufacture, DDXs in river sediment decreased by one order of magnitude since 1970's and low DDT fractions in these sediments were observed. Still, DDXs in the sediments near the outlets of the major manufacturers remained relatively high attributed to the historic input. DDXs in sediment were also positively correlated with organic matter content. Spatial distributions of DDXs in SS and water was different from that in sediment. For SS, a negative correlation between DDX concentration and SS content indicated a dilution effect in many rivers. Dissolved organic carbon content was the major factor affecting DDX concentrations in water phase. Wastewater discharged from dicofol manufacturers and likely illegal agricultural application were the primary reasons causing high DDT (DDE+DDD) ratios in SS and water.