Photoinitiated oxidation of geosmin and 2-methylisoborneol by irradiation with 254 nm and 185 nm UV light

The degradation of geosmin and 2-methylisoborneol (2-MIB) by UV irradiation at different wavelengths was investigated under varying boundary conditions. The results showed that conventional UV radiation (254 nm) is ineffective in removing these compounds from water. In contrast to the usual UV radiation UV/VUV radiation (254 + 185 nm) was more effective in the removal of the taste and odour compounds. The degradation could be described by a simple pseudo first-order rate law with rate constants of about 1.2 × 10⁻³ m² J⁻¹ for geosmin and 2-MIB in ultrapure water. In natural water used for drinking water abstraction the rate constants decreased to 2.7 × 10⁻⁴ m² J⁻¹ for geosmin and 2.5 × 10⁻⁴ m² J⁻¹ for 2-MIB due to the presence of NOM. Additionally, the formation of the by-product nitrite was studied. In the UV/VUV irradiation process up to 0.6 mg L⁻¹ nitrite was formed during the complete photoinitiated oxidation of the odour compounds. However, the addition of low ozone doses could prevent the formation of nitrite in the UV/VUV irradiation experiments.     

Mechanism and kinetics of sulfamethoxazole photocatalytic ozonation in water

The photocatalytic ozonation of sulfamethoxazole (SMT) has been studied in water under different experimental conditions. The effect of gas flow rate, initial concentration of ozone, SMT and TiO₂ has been investigated to establish the importance of mass transfer and chemical reaction. Under the conditions investigated the process is chemically controlled. Both, SMT and TOC kinetics have been considered. Fast and slow kinetic regime of ozone reactions have been observed for SMT and TOC oxidation, respectively. Application of different inhibitors allows for the establishment of reaction mechanism involving direct ozonation, direct photolysis, hydroxyl radical reactions and photocatalytic reactions. Rate constants of the direct reaction between ozone and protonated, non-protonated and anionic SMT species have been determined to be 1.71 × 10⁵, 3.24 × 10⁵ and 4.18 × 10⁵ M⁻¹ s⁻¹, respectively. SMT quantum yield at 313 nm was found to be 0.012 moles per Einstein at pH 5 and 0.003 moles per Einstein at pHs 7 and 9. Main contributions to SMT removal were direct ozone reaction, positive hole oxidation and hydroxyl radical reactions. For TOC removal, main contributions were due to positive hole oxidation and hydroxyl radical reactions.     

Temporal record of Pu isotopes in inter-tidal sediments from the northeastern Irish Sea

A depth profile of ²³⁹Pu and ²⁴⁰Pu specific activities and isotope ratios was determined in an inter-tidal sediment core from the Esk Estuary in the northeastern Irish Sea. The study site has been impacted with plutonium through routine radionuclide discharges from the Sellafield nuclear reprocessing plant in Cumbria, NW England. A pronounced sub-surface maximum of ~ 10 kBq kg^-1 was observed for ^239 + 240Pu, corresponding to the peak in Pu discharge from Sellafield in 1973, with a decreasing trend with depth down to ~ 0.04 kBq kg^-1 in the deeper layers. The depth profile of ^239 + 240Pu specific activities together with results from gamma-ray spectrometry for ¹³⁷Cs and ²⁴¹Am was compared with reported releases from the Sellafield plant in order to estimate a reliable sediment chronology. The upper layers (1992 onwards) showed higher ^239 + 240Pu specific activities than would be expected from the direct input of annual Sellafield discharges, indicating that the main input of Pu is from the time-integrated contaminated mud patch of the northeastern Irish Sea. The ²⁴⁰Pu/²³⁹Pu atom ratios ranged from ~ 0.03 in the deepest layers to > 0.20 in the sub-surface layers with an activity-weighted average of 0.181. The decreasing ²⁴⁰Pu/²³⁹Pu atom ratio with depth reflects the changing nature of operations at the Sellafield plant from weapons-grade Pu production to reprocessing spent nuclear fuel with higher burn-up times in the late 1950s. In addition, recent annual ²⁴⁰Pu/²³⁹Pu atom ratios in winkles collected during 2003-2008 from three stations along the Cumbrian coastline showed no significant spatial or temporal differences with an overall average of 0.204, which supports the hypothesis of diluted Pu input from the contaminated mud patch.     

Interactions of land use and dynamic river conditions on sorption equilibria between benthic sediments and river soluble reactive phosphorus concentrations

Within-river cycling of P is a crucial link between catchment pollution sources and the resulting ecological impacts and integrates the biogeochemistry and hydrodynamics of river systems. This study investigates benthic sediment P sorption in relation to river soluble reactive phosphorus (SRP) concentrations during high- to low-flow changes in a major mixed land use river system in NE Scotland. We hypothesised that sediments comprised P sinks during moderate to higher flows but became P saturated with loss of buffering function during prolonged baseflow. Sediment characteristics were evaluated and equilibrium P concentrations (EPC₀) calculated using a standardised batch adsorption method (EPC₀ values 0.04-1.75 μmol P l⁻¹). Pollution-impacted tributaries (32-69% catchment agricultural land cover) had increased SRP concentrations (0.19-2.62 μmol P l⁻¹) and maintained EPC₀ < SRP values during changing flow conditions. Moorland-dominated tributaries and main stem sites had small SRP concentrations (0.03-0.19 μmol P l⁻¹) but showed EPC₀ > SRP values during summer baseflow so that sediments were indicated as P sources. This deviation from a geochemical sediment-water P equilibrium was attributed to biological accumulation of P from the water column into the sediments. In particular, large stores of sediment P accumulated in main stem reaches below agricultural tributaries and this may be consequential for sensitive downstream ecosystems. Hence, biogeochemical processes at the river bed may strongly influence river SRP cycling between geochemical and biotic pools. The nature of this internal reservoir of river P and its ecosystem interactions needs better understanding to enable best results to be attained from catchment mitigation actions designed to maintain/improve ecological status under the Water Framework Directive.     

Fast atrazine photodegradation in water by pulsed light technology

Pulsed light technology consists of a successive repetition of short duration (325 μs) and high power flashes emitted by xenon lamps. These flashlamps radiate a broadband emission light (approx. 200-1000 nm) with a considerable amount of light in the short-wave UV spectrum. In the present work, this technology was tested as a new tool for the degradation of the herbicide atrazine in water. To evaluate the presence and evolution with time of this herbicide, as well as the formation of derivatives, liquid chromatography-mass spectrometry (electrospray ionization) ion trap operating in positive mode was used. The degradation process followed first-order kinetics.Fluences about1.8-2.3 J/cm² induced 50% reduction of atrazine concentration independently of its initial concentration in the range 1-1000 μg/L. Remaining concentrations of atrazine, below the current legal limit for pesticides, were achieved in a short period of time. While atrazine was degraded, no chlorinated photoproducts were formed and ten dehalogenated derivatives were detected. The molecular structures for some of these derivatives could be suggested, being hydroxyatrazine the main photoproduct identified. The different formation profiles of photoproducts suggested that the degradation pathway may include several successive and competitive steps, with subsequent degradation processes taking part from the already formed degradation products. According to the degradation efficiency, the short treatment time and the lack of chloroderivatives, this new technology could be considered as an alternative for water treatment.     

Anatoxin-a degradation by Advanced Oxidation Processes: Vacuum-UV at 172 nm, photolysis using medium pressure UV and UV/H2O2

Two Advanced Oxidation Processes, namely vacuum-ultraviolet (VUV) photolysis at 172 nm and ultraviolet/hydrogen peroxide (UV/H₂O₂) were investigated for the degradation of anatoxin-a in aqueous solutions. Solutions of anatoxin-a-fumarate were treated with VUV light at 172 nm with a UV dose of 200 mJ/cm², where fumaric acid served as a reference compound for a competition kinetics analysis. The second-order rate constant for the reaction between anatoxin-a and the hydroxyl radical was found to be (5.2 ± 0.3) × 10⁹ M⁻¹ s⁻¹ and was independent of pH, temperature, and initial concentration of anatoxin-a. The direct photolysis of anatoxin-a using a medium pressure (MP) UV lamp was also investigated, in which case a UV dose of 1285 mJ/cm² was required to degrade anatoxin-a by 88% and 50% at concentrations of 0.6 mg/L and 1.8 mg/L of toxin, respectively. Treatment of anatoxin-a with a low pressure (LP) UV lamp in the presence of 30 mg/L of H₂O₂ was examined, where it was found that more than 70% of toxin could be degraded at a UV dose of 200 mJ/cm². The degradation arises from the oxidation of the toxin by hydroxyl radicals. The addition of H₂O₂ clearly enhanced the degradation of anatoxin-a, up to a concentration of 40 mg/L, after which addition of more H₂O₂ had little effect on the degradation kinetics of anatoxin-a. The effect of background constituents in the water on the degradation of anatoxin-a was also investigated using natural and synthetically produced model waters.     

Freshwater DOM quantity and quality from a two-component model of UV absorbance

We present a model that considers UV-absorbing dissolved organic matter (DOM) to consist of two components (A and B), each with a distinct and constant spectrum. Component A absorbs UV light strongly, and is therefore presumed to possess aromatic chromophores and hydrophobic character, whereas B absorbs weakly and can be assumed hydrophilic. We parameterised the model with dissolved organic carbon concentrations [DOC] and corresponding UV spectra for c. 1700 filtered surface water samples from North America and the United Kingdom, by optimising extinction coefficients for A and B, together with a small constant concentration of non-absorbing DOM (0.80 mg DOC L⁻¹). Good unbiased predictions of [DOC] from absorbance data at 270 and 350 nm were obtained (r² = 0.98), the sum of squared residuals in [DOC] being reduced by 66% compared to a regression model fitted to absorbance at 270 nm alone. The parameterised model can use measured optical absorbance values at any pair of suitable wavelengths to calculate both [DOC] and the relative amounts of A and B in a water sample, i.e. measures of quantity and quality. Blind prediction of [DOC] was satisfactory for 9 of 11 independent data sets (181 of 213 individual samples).     

Protection against UV disinfection of E. coli bacteria and B. subtilis spores ingested by C. elegans nematodes

Nematodes, which occur abundantly in granular media filters of drinking water treatment plants and in distribution systems, can ingest and transport pathogenic bacteria and provide them protection against chemical disinfectants. However, protection against UV disinfection had not been investigated to date.In this study, Caenorhabditis elegans nematodes (wild-type strain N2) were allowed to feed on Escherichia coli OP50 and Bacillus subtilis spores before being exposed to 5 and 40 mJ/cm² UV fluences, using a collimated beam apparatus (LP, 254 nm). Sonication (15 W, 60 s) was used to extract bacteria from nematode guts following UV exposure in order to assess the amount of ingested bacteria that resisted the UV treatment using a standard culture method. Bacteria located inside the gut of C. elegans were shown to benefit from a significant protection against UV. Approximately 15% of the applied UV fluence of 40 mJ/cm² (as typically used in WTP) was found to reach the bacteria located inside nematode guts based on the inactivation of recovered bacteria (2.7 log reduction of E. coli bacteria and 0.7 log reduction of B. subtilis spores at 40 mJ/cm²). To our knowledge, this study is the first demonstration of the protection effect of bacterial internalization by higher organisms against UV treatment, using the specific case of E. coli and B. subtilis spores ingested by C. elegans.     

Environmental occurrence, fate and transformation of benzodiazepines in water treatment

Benzodiazepine derivatives are prescribed in large quantities globally and are potentially new emerging environmental contaminants. Unfortunately, a dearth of data exists concerning occurrence, persistence and fate in the environment. This paper redresses this by reviewing existing literature, assessing the occurrence of selected benzodiazepine anxiolytics (diazepam, oxazepam and bromazepam) in wastewater influent and effluent and surface water from Slovenia, evaluating their removal during water treatment and identifying the transformation products formed during water treatment. Their occurrence was monitored in hospital effluent, river water and in wastewater treatment plant influent and effluent. The study reveals the presence of benzodiazepine derivatives in all samples with the highest amounts in hospital effluents: 111 ng L⁻¹, 158 ng L⁻¹ and 72 ng L⁻¹ for diazepam, bromazepam and oxazepam, respectively. Removal efficiencies with respect to biological treatment of diazepam were 16-18% (oxic), 18-32% (anoxic → oxic), 53-76% (oxic → anoxic) and 83% (oxic → anoxic → oxic → anoxic cascade bioreactors), while the removal oxazepam was 20-24% under anoxic conditions. Coupled biological and photochemical treatment followed by the adsorption to activated carbon resulted in a removal efficiency of 99.99%. Results reveal the recalcitrant nature of benzodiazepine derivatives and suggest that only combinational treatment is sufficient to remove them. In addition, eight novel diazepam and four novel oxazepam transformation products are reported.     

A comparison of the isotopic composition of lead in rainwater, surface vegetation and tree bark at the long-term monitoring site, Glensaugh, Scotland, in 2007

The lead concentrations and isotopic ratios (²⁰⁶Pb/²⁰⁷Pb, ²⁰⁸Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁷Pb) of 31 rainwater (September 2006-December 2007) and 11 surface vegetation (moss, lichen, heather) samples (October 2007) from the rural upland catchment of Glensaugh in northeast Scotland and of nine bark samples (October 2007) from trees, predominantly Scots pine, in or near Glensaugh were determined. The mean ²⁰⁶Pb/²⁰⁷Pb ratios for rainwater in 2006 and 2007 were similar to those previously determined for 2000 to 2003 at Glensaugh, yielding an average mean annual value of 1.151 ± 0.005 (± 1 SD) for the period from 2000, when an outright ban on leaded petrol came into force in the UK, to 2007. The mean ²⁰⁶Pb/²⁰⁷Pb ratio (1.146 ± 0.004; n = 7) for surface vegetation near the top (430-450 m) of the catchment was not significantly different (Student's t test) from that of rainwater (1.148 ± 0.017; n = 24) collected over the 12-month period prior to vegetation sampling, but both were significantly different, at the 0.1% (i.e. p < 0.001) and 1% (p < 0.01) level, respectively, from the corresponding mean value (1.134 ± 0.006; n = 9) for the outermost layer of tree bark. When considered in conjunction with similar direct evidence for 2002 and indirect evidence (e.g. grass, atmospheric particulates, dated peat) for recent decades in the Glensaugh area, these findings confirm that the lead isotopic composition of surface vegetation, including that of suitably located moss, reflects that of the atmosphere while that of the outermost layer of Scots pine bark is affected by non-contemporaneous lead. The nature and relative extent of the different contributory sources of lead to the current UK atmosphere in the era of unleaded petrol, however, are presently not well characterised on the basis of lead isotopic measurements.     

Distribution of (210)Pb and (210)Po in boreal forest soil

Vertical distribution and activity contents of ²¹⁰Pb and ²¹⁰Po were investigated in forest soils of Scots pine-dominated (Pinus sylvestris L.) stands from seven different locations in Finland. The mean total inventory in the soil profile, up to 20 cm, of ²¹⁰Pb was 4.0 kBq m^− 2 (range 3.1-5.0 kBq m^− 2) and ²¹⁰Po 5.5 kBq m^− 2 (range 4.0-7.4 kBq m^− 2), the organic soil layer containing 45% of the total inventory of both nuclides. In both the organic and the mineral layers the ²¹⁰Po/²¹⁰Pb ratio was close to unity indicating a radioactive equilibrium between them. In the litter layer there was, however, a clear excess of ²¹⁰Po suggesting that polonium is recycled via root uptake from the root zone to the ground surface. The activity concentration (Bq kg^− 1) of ²¹⁰Pb clearly correlated with organic matter and the Fe, Al and Mn concentrations in soil indicating that radioactive lead is associated both with humic substances and the oxides of iron, aluminium and manganese. Radioactive lead was also seen to follow the behavior of stable lead. No systematic correlation between polonium and soil properties was seen.     

The origin of lead in the organic horizon of tundra soils: atmospheric deposition, plant translocation from the mineral soil or soil mineral mixing?

Knowledge of the anthropogenic contribution to lead (Pb) concentrations in surface soils in high latitude ecosystems is central to our understanding of the extent of atmospheric Pb contamination. In this study, we reconstructed fallout of Pb at a remote sub-arctic region by using two ombrotrophic peat cores and assessed the extent to which this airborne Pb is able to explain the isotopic composition (²⁰⁶Pb/²⁰⁷Pb ratio) in the O-horizon of tundra soils. In the peat cores, long-range atmospheric fallout appeared to be the main source of Pb as indicated by temporal trends that followed the known European pollution history, i.e. accelerated fallout at the onset of industrialization and peak fallout around the 1960s-70s. The Pb isotopic composition of the O-horizon of podzolic tundra soil (²⁰⁶Pb/²⁰⁷Pb = 1.170 ± 0.002; mean ± SD) overlapped with that of the peat (²⁰⁶Pb/²⁰⁷Pb = 1.16 ± 0.01) representing a proxy for atmospheric aerosols, but was clearly different from that of the parent soil material (²⁰⁶Pb/²⁰⁷Pb = 1.22-1.30). This finding indicated that long-range fallout of atmospheric Pb is the main driver of Pb accumulation in podzolic tundra soil. In O-horizons of tundra soil weakly affected by cryoturbation (cryosols) however, the input of Pb from the underlying mineral soil increased as indicated by ²⁰⁶Pb/²⁰⁷Pb ratios of up to 1.20, a value closer to that of local soil minerals. Nevertheless, atmospheric Pb appeared to be the dominant source in this soil compartment. We conclude that Pb concentrations in the O-horizon of studied tundra soils - despite being much lower than in boreal soils and representative for one of the least exposed sites to atmospheric Pb contaminants in Europe - are mainly controlled by atmospheric inputs from distant anthropogenic sources.     

An initial study to assess the use of geological parent materials to predict the Se concentration in overlying soils and in five staple foodstuffs produced on them in Scotland

Evidence suggests that dietary-intakes of the essential element selenium have fallen in Scotland in recent years, due to changing sources of bread-making wheat. The Scottish environment is thought to be Se-poor due to the geology and climate. This initial study assessed whether geological parent-materials could be used to predict relatively high and low soil-Se areas in Scotland and whether differences in soil-Se were reflected in foodstuff-Se produced on them. Samples (n = 8 per farm) of wheat, calabrese (broccoli), potato, beef-steak, milk, cattle pasture (grass) and soil were collected from pairs of farms (one in each high/low predicted Se area (PSA)). Potatoes and soils were collected from a further 34 farms in high/low PSAs to assess a greater geographical zone. Total soil-Se ranged from 0.115 to 0.877 mg kg^-1 but most samples (90%) could be classed as Se-deficient (< 0.6 mg kg⁻¹), irrespective of PSA. Total soil-Se was significantly higher (p < 0.05) in the high than in the low PSAs as expected; however, the difference between the two was small (mean 0.48 and 0.37 mg kg⁻¹, respectively). Water-soluble soil-Se (6.69 to 26.78 μg kg⁻¹) concentrations were not significantly different between the two PSAs (p = 0.71). Soil loss-on-ignition (indicating organic matter content) correlated significantly with total and water-soluble soil-Se (p < 0.001) and exerted a greater control than parent-material on soil-Se. Significant differences between the PSAs for beef-Se (p < 0.001), wheat-Se (p < 0.001), calabrese-Se (p < 0.01) and beef-farm grass-Se (p < 0.05) indicated partial success of the parent-material soil-Se prediction. However, only wheat-Se (p < 0.001) and potato-Se (p < 0.001) correlated significantly with total soil-Se. The results suggest that soil-Se concentrations in the main agricultural areas of Scotland are generally low. Given the low Se concentrations also reported in the food commodities; further investigations may be warranted to fully characterise the Se-status of Scottish produce and dietary-Se intakes in Scotland.     

Oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol by means of Fe(III)-homogeneous photocatalysis and algal toxicity assessment of the treated solutions

Chlorophenols are used worldwide as broad-spectrum biocides and fungicides. They have half-life times in water from 0.6 to 550 h and in sediments up to 1700 h and, due to their numerous origins, they can be found in wastewaters, groundwaters or soils. Moreover, chlorophenols are not readily biodegradable.Recently, classic Advanced Oxidation Processes (AOP) have been proposed for their abatement in an aqueous solution. This paper investigates the oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol, at starting concentrations of 6.1 · 10⁻⁵ mol L⁻¹, in aqueous solutions through Fe(III)/O₂ homogeneous photocatalysis under UV light (303 ÷ 366 nm). The Fe(III)/O₂ homogeneous photocatalysis is less expensive than using H₂O₂ due to the capability of Fe(III) to produce OH radicals, if irradiated with an UVA radiation, and of oxygen to re-oxidize ferrous ions to ferric ones when dissolved in solution. The results show that the best working conditions, for both compounds, are found for pH = 3.0 and initial Fe(III) concentration equal to 1.5·10⁻⁴ mol L⁻¹ although the investigated oxidizing system can be used even at pH close to 4.0 but with slower abatement kinetics. Toxicity assessment on algae indicates that treated solutions of 2,4-dichlorophenol are less toxic on algae Pseudokirchneriella subcapitata if compared to not treated solutions whereas in the case of 3,4-dichlorophenol only the samples collected during the runs at 20 and 60 min are capable of inhibiting the growth of the adopted organism.The values of the kinetic constant for the photochemical re-oxidation of iron (II) to iron (III) and for HO attack to intermediates are evaluated by a mathematical model for pH range of 2.0-3.0 and initial Fe(III) concentrations range of 1.5 · 10⁻⁵-5.2 · 10⁻⁴ mol L⁻¹.     

Electrocatalytic characterization and dye degradation of Nano-TiO2 electrode films fabricated by CVD

A 20-40 nm anatase-titania film on a titanium electrode was fabricated using chemical vapor deposition (CVD). The film was characterized using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and atomic force microscopy (AFM). The CVD deposition time and number of deposition coatings were evaluated to establish the appropriate film fabrication parameters. Results indicate that two coatings at a deposition time of 6 h each produced the best nano-TiO₂ electrode films (NTEFs) with an even distribution of ca. 20 nm diameter nanoparticles in the anatase lattice. The NTEF was tested as an electrocatalytic anode to investigate the degradation efficiency in treating methyl orange dye wastewater. A high removal efficiency of methyl orange dye and total organic carbon (TOC) of 97 and 56%, respectively; was achieved using a current density of 20 mA cm^− 2 for 160 min. Cyclic voltammetry showed that the electrochemical degradation reaction rate at the NTEF surface was predominately driven by molecular diffusion. The electrocatalytic decomposition rate of organic pollutants at the NTEF is controlled by mass transport, which was associated with the nanostructure of the electrocatalytic electrode.     

Determination of aromatic amines in water samples by capillary electrophoresis with amperometric detection

Aromatic amines such as aniline and its derivatives are an important class of environmental water pollutants. A method based on capillary zone electrophoresis with amperometric detection (CZE-AD) at carbon disk electrode was developed for the determination of aromatic amines in water samples. The effects of working potential, pH and concentration of running buffer, separation voltage and injection time were investigated. Under the optimum conditions, 2,3-diaminonaphthalene, aniline, o-phenylenediamine and p-chloroaniline could be separated in 0.16 mol/L Na₂HPO₄-citric acid buffer (pH 4.6) within 23 min. The detection limits of them were 1.0 × 10⁻⁷, 3.3 × 10⁻⁸, 5.0 × 10⁻⁸, and 1.3 × 10⁻⁷ mol/L (S/N = 3), respectively. The method can be applied directly for the determination of aromatic amines in real water samples with satisfactory results.     

Anthropogenic acidification effects in primeval forests in the Transcarpathian Mts., western Ukraine

The precipitation chemistry, deposition, nutrient pools and composition of soils and soil water, as well as an estimate of historical deposition of sulphur (S) and inorganic nitrogen (N) for the period 1860-2008, were determined in primeval deciduous and coniferous forests at the sites Javornik and Pop Ivan, respectively. Measured S throughfall inputs of 10 kg ha^− 1 year^− 1 in 2008 were similar to those estimated for the period 1900-1950 at both sites. The highest estimated S inputs were in the 1980s. Measured bulk deposition of N in 2008 was lower at Pop Ivan (5.6 kg ha^− 1 year^− 1) compared to Javornik (12 kg ha^− 1 year^− 1). Significantly lower NO₃ deposition was both estimated and measured at Pop Ivan. Higher soil base cation concentrations were observed at well-buffered Javornik underlain by flysch (Ca pool of 2046 kg ha^− 1 and base saturation of 29%) compared to Pop Ivan underlain by crystalline schist (Ca pool of 186 kg ha^− 1 and base saturation of 6.5%). The soil pool of organic carbon (C) was higher at Pop Ivan (212 t ha^− 1) compared to Javornik (127 t ha^− 1). The C concentration was positively correlated with organic N in the soil (p < 0.001) at both sites, but the mass average C/N ratio in the forest floor was lower at Javornik (22) than at Pop Ivan (26). High N leaching of 17 kg ha^− 1 year^− 1 at the 90 cm depth was measured in the soil water at Javornik, suggesting high mineralization and nitrification rates in old growth deciduous forests in the area. Despite relatively low Al concentrations in the soil water, a low soil water Bc/Al ratio (0.9) (Bc = Ca + Mg + K) was found in the upper mineral soil at Pop Ivan. This suggests that the spruce forest ecosystems in the area are vulnerable to anthropogenic acidification and to the adverse effects of Al on forest root systems.     

Strategies for lipids and phenolics degradation in the anaerobic treatment of olive mill wastewater

Strategies are proposed for the anaerobic treatment of lipid and phenolic-rich effluents, specifically the raw olive mill wastewater (OMW). Two reactors were operated under OMW influent concentrations from 5 to 48 g COD L⁻¹ and Hydraulic Retention Time between 10 and 5 days. An intermittent feeding was applied whenever the reactors showed a severe decay in the methane yield. This strategy improved the mineralization of oleate and palmitate, which were the main accumulated Long-Chain Fatty Acids (LCFA), and also promoted the removal of resilient phenolic compounds, reaching remarkable removal efficiencies of 60% and 81% for two parallel reactors at the end of a feed-less period. A maximum biogas production of 1.4 m³ m⁻³ d⁻¹ at an Organic Loading Rate of 4.8 kg COD m⁻³ d⁻¹ was obtained. Patterns of individual LCFA oxidation during the OMW anaerobic digestion are presented and discussed for the first time. The supplementation of a nitrogen source boosted immediately the methane yield from 21 and 18 to 76 and 93% in both reactors. The typical problems of sludge flotation and washout during the anaerobic treatment of this oily wastewater were overcome by biomass retention, according to the Inverted Anaerobic Sludge Blanket (IASB) reactor concepts. This work demonstrates that it is possible to avoid a previous detoxification step by implementing adequate operational strategies to the anaerobic treatment of OMW.     

Free-radical-induced oxidative and reductive degradation of N,N′-diethyl-m-toluamide (DEET): Kinetic studies and degradation pathway

N,N′-Diethyl-m-toluamide (DEET) is widely used as an insect repellent and has therefore been detected as a contaminant in numerous waste and surface waters. In this study we have determined the absolute reaction rate constants of DEET with the hydroxyl radical and the hydrated electron in aqueous solution as (4.95 ± 0.18) × 10⁹ and (1.34 ± 0.04) × 10⁹ M⁻¹ s⁻¹, respectively, using pulse radiation. To provide additional information on the radicals formed upon oxidation, transient spectra were measured from 1 to 150 μs, with transient decay rates determined from the time-dependence of the maximum absorption at 330 nm. These data suggest simple decay of the initially formed radical to stable products. Radical-based destruction mechanisms for destruction of DEET are proposed based on the LC-MS determination of the stable compounds produced by ⁶⁰Co γ-irradiation of DEET solutions. These data will be useful in evaluating potential advanced oxidation/reduction processes for the control of DEET and understanding its fate and transport in surface water where analogous radical chemistry is operative.     

A lead isotopic study of the human bioaccessibility of lead in urban soils from Glasgow, Scotland

The human bioaccessibility of lead (Pb) in Pb-contaminated soils from the Glasgow area was determined by the Unified Bioaccessibility Research Group of Europe (BARGE) Method (UBM), an in vitro physiologically based extraction scheme that mimics the chemical environment of the human gastrointestinal system and contains both stomach and intestine compartments. For 27 soils ranging in total Pb concentration from 126 to 2160 mg kg^− 1 (median 539 mg kg^− 1), bioaccessibility as determined by the ‘stomach’ simulation (pH ~ 1.5) was 46-1580 mg kg^− 1, equivalent to 23-77% (mean 52%) of soil total Pb concentration. The corresponding bioaccessibility data for the ‘stomach + intestine’ simulation (pH ~ 6.3) were 6-623 mg kg^− 1 and 2-42% (mean 22%) of soil Pb concentration. The soil ²⁰⁶Pb/²⁰⁷Pb ratios ranged from 1.057 to 1.175. Three-isotope plots of ²⁰⁸Pb/²⁰⁶Pb against ²⁰⁶Pb/²⁰⁷Pb demonstrated that ²⁰⁶Pb/²⁰⁷Pb ratios were intermediate between values for source end-member extremes of imported Australian Pb ore (1.04) - used in the manufacture of alkyl Pb compounds (1.06-1.10) formerly added to petrol - and indigenous Pb ores/coal (1.17-1.19). The ²⁰⁶Pb/²⁰⁷Pb ratios of the UBM ‘stomach’ extracts were similar (< 0.01 difference) to those of the soil for 26 of the 27 samples (r = 0.993, p < 0.001) and lower in 24 of them. A slight preference for lower ²⁰⁶Pb/²⁰⁷Pb ratio was discernible in the UBM. However, the source of Pb appeared to be less important in determining the extent of UBM-bioaccessible Pb than the overall soil total Pb concentration and the soil phases with which the Pb was associated. The significant phases identified in a subset of samples were carbonates, manganese oxides, iron-aluminium oxyhydroxides and clays.