Recently, metal nanoparticles have attracted attention as promising peroxygen activators for the rapid and effective remediation of organic contaminants. In this work, a one-dimensional physical model experiment was designed to investigate the mobility of the metal nanoparticles in porous media and the potential use of metal nanoparticles as peroxygen activators for in situ treatment of source zones. We found that our synthesized nano-Pd-Fe0 particles were mobile in a non-geological porous medium and relatively immobile in a geological porous medium. In addition, we observed that iron-based bimetallic nanoparticles were able to remain in suspension in an ideal aqueous system much longer (>6 weeks) than iron-based monometallic nanoparticles (<1 h). To overcome the nano-Pd-Fe0 particle delivery issue in geological porous media, an activation zone approach was adopted. Nano-Pd-Fe0 particles were injected in order to create a zone to activate persulfate for the treatment of a trichloroethylene source zone. Trichloroethylene mass destruction was only 9 % higher in the nano-Pd-Fe 0 activated persulfate system compared to the non-activated persulfate system as revealed by a short-duration chloride concentration spike in the effluent. In addition, the nano-Pd-Fe0 activation zone was rapidly deactivated after being exposed to persulfate as visually observed by a color change, indicating that the longevity of the activation zone is limited. © 2013 Springer Science+Business Media Dordrecht.

In the present paper, undoped and Ni-doped TiO2 sol-gel nanopowders have been prepared in order to establish the effect of Ni dopant on both material structure and photocatalytic properties. Two dopant concentrations of the transition metal (0.5 and 2 wt%) have been tested. The influence of both Ni dopant concentration and temperature of thermal treatment on the prepared powders has been followed using X-ray diffraction (XRD) method. A proper program has been used in order to establish the complete XRD structural characterization (lattice parameters, crystrallite sizes, internal strains). X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM) coupled with surface area electron diffraction (SAED) techniques have completed the structural and morphological characterization of the prepared materials. Magnetic measurements and photocatalytic activity determinations have also been performed. The correlation between the results of the mentioned methods has been accomplished, and the detailed interpretation of the relation between structure and photocatalytic activity measurements has been done. The concentration of 0.5 wt% of Ni dopant ensures a better photocatalytic activity, compared to that of 2 wt%. © 2013 Springer Science+Business Media Dordrecht.

Biomonitoring of atmospheric ammonia (NH₃) concentrations is generally performed with epiphytic lichens, using species’ abundances and/or nitrogen concentration as monitoring tools. However, the potential of leaf characteristics of trees to monitor the atmospheric NH₃ concentration has remained largely unexplored. Therefore, we performed a passive biomonitoring study with common oak (Quercus robur L.) at 34 sampling locations in the near vicinity of livestock farms, located in Flanders (northern Belgium). We aimed at evaluating the potential of specific leaf area, leaf area fluctuating asymmetry, stomatal resistance, and chlorophyll content of common oak to monitor a broad range of NH₃ concentrations (four-monthly average of 1.9–29.9 μg m⁻³). No significant effects of ambient NH₃ concentration on the abovementioned leaf characteristics were revealed. Probably, differences in climate, soil characteristics, and concentrations of other air pollutants and/or genotypes confounded the influence of NH₃. Consequently, this study demonstrates the inability of using these morphological, anatomical, and physiological common oak leaf characteristics to monitor ambient NH₃ concentration.

Rewetting of agriculturally used peatlands has been proposed as a measure to stop soil subsidence, conserve peat and rehabilitate ecosystem functioning. Unintended consequences might involve nutrient release and changes in the greenhouse gas (GHG) balance towards CH₄-dominated emission. To investigate the risks and benefits of rewetting, we subjected soil columns from drained peat- and clay-covered peatlands to different water level treatments: permanently low, permanently inundated and fluctuating (first inundated, then drained). Surface water and soil pore water chemistry, soil-extractable nutrients and greenhouse gas fluxes were measured throughout the experiment. Permanent inundation released large amounts of nutrients into pore water, especially phosphorus (up to 11.7 mg P-PO₄ l⁻¹) and ammonium (4.8 mg N-NH₄ l⁻¹). Phosphorus release was larger in peat than in clay soil, presumably due to the larger pool of iron-bound phosphorus in peat. Furthermore, substantial amounts of phosphorus and potassium were exported from the soil matrix to the surface water, risking the pollution of local species-rich (semi-)aquatic ecosystems. Rewetting of both clay and peat soil reduced CO₂ emissions. CH₄ emissions increased, but, in contrast to the expectations, the fluxes were relatively low. Calculations showed that rewetting reduced net cumulative GHG emissions expressed as CO₂ equivalents.

The fate and behaviour of tributyltin (TBT) at two wastewater treatment works was examined. Both sites had two inlet streams, and each utilised high rate biological filters (biofilters) on one the streams, before treatment of the combined flows on trickling filters, with one having additional tertiary processes, installed to remove ammonia and solids. The study was designed to determine if these processes enhanced the removal of TBT. Degradation of TBT was observed in one of the biofilters, possibly as a result of temperature and hydraulic loading. At the treatment works with tertiary processes, the mass flux showed the overall removal of TBT was 68 %, predominantly due to removal with solids in the primary settlement processes. However, overall removal of 95 % was observed in the conventional trickling filter works with 94 % of this due to biodegradation in the trickling filter. The two works both removed TBT, but at different treatment stages and by different processes. Differences in the form (solubility) of TBT in the influent may have attributed to this, although further understanding of factors controlling degradation would allow for a more complete assessment of the potential of biological processes to remove hazardous compounds from wastewaters.

Acid mine drainage (AMD) generated by some coal mines in New Zealand is currently treated by the addition of alkaline reagents which neutralize acidity, triggering the precipitation of dissolved metals as insoluble hydroxides. Some trace metals (Ni, Zn, Cu, Cd, and Pb) are discharged into receiving water bodies due to incomplete hydroxide precipitation at circum-neutral pH. This study investigated the incorporation of lignite-derived humic substances (HS) for metal complexation and removal during AMD treatment by Ca(OH)₂ and CaCO₃ neutralization. For Ca(OH)₂ neutralization, addition of HS (regardless of dosing sequence) enhanced the removal of Zn, Cu, and Cd, probably due to the incorporation of metal–humate complex into settling flocs (via aggregation, co-precipitation, and adsorption) that were subsequently removed by sedimentation. However, additional removal of Ni and Pb was statistically indeterminate, which was ascribed to the low complexation affinity of Ni and high removal of Pb by adsorption onto Fe/Al hydroxides. Conversely, for CaCO₃ neutralization, addition of HS only marginally enhanced Cd removal, with the removal of metals probably dominated by adsorption onto the abundant undissolved calcite. Equilibrium speciation modelling showed that about 25% and 38% of the remaining Cu and Pb in the treated AMD were complexed with HS, while only 5% of remaining Cd and less than 1 wt% of remaining Ni and Zn were organically complexed. In the AMD-receiving water bodies, about 20 mg l⁻¹ of HS would be required for complete complexation (>95%) of Cu and Pb and 50 mg l⁻¹ for Cd, whereas Zn and Ni complexation would not occur at natural stream HS concentrations.

The flux of metals at the tidal limits of major rivers are an important metric of freshwater contaminant transfer to marine habitats, reported in Northeast Atlantic bordering countries under the 1992 Oslo-Paris (OSPAR) Convention. This paper presents an assessment of long-term OSPAR data for four trace metals (Cd, Cu, Pb, and Zn) using a range of spatial datasets to assess the broad distribution of metal flux and yield across England and Wales. Mine site records and geological and land use data are used to classify river basins into six classes. The bulk of metal flux to seas around England and Wales occurs from catchments containing extensive mineralization and a legacy of metal mining (52 % of the total Zn flux, 47 % of Pb, 39 % of Cu, and 48 % of Cd were associated with mined catchments). Catchment area, metal flux from point mine discharges at source, and extent of mineralization typically accounted most for variation in catchment outlet metal flux in stepwise multiple linear regression (SMLR). There are a number of small mining-impacted rural catchments contributing significant fluxes of metals to coastal waters. Of particular prominence are Restronguet Creek (drainage area 87 km²) in southwest England that discharges 176 t Zn/year and 18 t Cu/year and the Afon Goch Dulas (27 km²) in north Wales, which releases 20 t Zn/year and 9 t Cu/year. Although such exercises cannot directly determine the provenance of metals, comparison with metal release data and a review of catchment-scale studies suggest a critical role of mining-related contaminants in contributing to catchment metal export.

The occurrence of 16 pharmaceutical compounds in river sediments from Donana National Park was investigated, as well as the ecotoxicological risk to the ecosystems of this well-known protected zone. Eight of the 16 pharmaceuticals were present in sediments. The highest concentrations in river sediments concern to diclofenac, salicylic acid and caffeine (52.1, 27.2 and 25.4 mu g/kg dm). Naproxen, carbamazepine, propranolol, 17 beta-estradiol and estriol were the other pharmaceutical compounds detected in sediment samples. The relation between the concentration of these pharmaceutical compounds in sediments and river water in contact with was also investigated. While some compounds were detected exclusively in sediment samples (diclofenac, 17 beta-estradiol and estriol), others were detected only in surface waters in contact with (ibuprofen, ketoprofen and gemfibrozil). The outcome analyses of the ecotoxicological risk assessment showed that the presence of all studied pharmaceutical compounds involved a high toxicological risk at short and long term to Donana ecosystem.

Sepiolite reveals as a low-cost and efficient adsorbent for the adsorption of caffeine from aqueous solutions. The characterization of this material was carried out by N₂ adsorption–desorption at 77 K, Fourier transform infrared spectroscopy, thermogravimetric analysis, and electronic microscopy. Initially, batch adsorption experiments were developed in order to determine the equilibrium time and the adsorption isotherm of the system. Pseudo–first-order, Elovich equation, pseudo–second-order, and intra-particle diffusion models were applied to the experimental data to determine the adsorption kinetics. In continuous adsorption, the influence of several operation conditions (initial caffeine concentration, volumetric flow rate, and mass of adsorbent) on the shape of breakthrough curves and the mass transfer resistance was evaluated. Experimental data were fitted to the bed-depth service-time model bed-depth service-time (BDST). Through the calculation of the adsorption, parameters as breakthrough time or caffeine removal percentage can be concluded that the removal of this compound from aqueous solutions by adsorption in sepiolite beds is an alternative technique to the current methods, in order to eliminate this micropollutant.

A comparative long-term study of three subsurface horizontal-flow (HF) constructed wetlands (CW) treating winery wastewater was carried out. The water depth for HF1 was 0.3 m, while the depth for HF2 and HF3 was 0.6 m, respectively. Hydraulic loading rate ranged from 7 to 93 mm/d, while surface loading rates fell into the following ranges: 4–85 g COD/m²·d, 2–49 g BOD₅/m²·d and 0.5–6 g TSS/m²·d. The percentage of biological oxygen demand (BOD₅) removal clearly decreased when influent concentration increased, while surface removal rate increased and reached a maximum of approximately 8 g BOD₅/m²·d removed in the range of 10–20 g BOD₅/m²·d fed, depending on the CW depth. HF1 showed a worse performance than the other units, appearing to be more affected by high influent concentrations. Solids accumulation on gravel media, hydraulic conductivity and gas emissions were monitored over the 2.8 years of operation.