In this study, the degradation of molinate through heterogeneous photocatalysis, using two different types of the semiconductor TiO₂ as photocatalyst, as well as through homogeneous treatment, applying the photo-Fenton reaction, has been investigated. As far as heterogeneous photocatalysis is concerned, the degradation of the pesticide follows apparent first-order kinetics, while the type of the catalyst and the pH value of the solution affect the degradation rate. The effect of the addition of electron scavengers (H₂O₂ and K₂S₂O₈) was also studied. In the case of photo-Fenton-assisted system, the degradation also follows pseudo-first-order kinetics. Parameters such as iron’s and electron scavenger’s concentration and inorganic ions strongly affect the degradation rate. The extent of pesticide mineralization was investigated using dissolved organic carbon (DOC) measurements. The toxicity of the treated solution was evaluated using the Microtox test based on the luminescent bacteria Vibrio fischeri. The detoxification and mineralization efficiency was found to be dependent on the system studied, and although it did not follow the rate of pesticide disappearance, it took place in considerable extent. The study of the photodegradation treatment was completed by the determination of the intermediate by-products formed during the process, which was carried out using LC-MS/MS technique and led to similar compounds with both processes.

The relevance of a risk assessment of the built heritage was clearly justified due to the fact that it acts as a pollutant repository and hazardous pollutants have the capacity to penetrate into materials. However, the limitation of the sampling processes due to the high value of the built heritage makes a correct evaluation difficult. For that reason, in the present work, the potential of agar gels as non-invasive samplers of built heritage deterioration products, like crusts and patinas, was evaluated. Different gels of agar and Carbopol® (as control gel) were applied on these built surfaces considering several factors: the treatment time, the effectiveness of the addition of EDTA (ethylenediaminetetraacetic acid, C₁₀H₁₆N₂O₈) and its concentration and the use of a buffer at pH 7.5. All these factors were evaluated in order to determine the capacity of these gels as sampling systems under non-controlled atmospheric conditions. The results obtained in the assays were evaluated by visual examination, by evolution of pH and by the most important techniques used in the risk assessment analysis of the built heritage (Raman spectroscopy, scanning electron microscope (SEM)/energy dispersive X-ray (EDX) and inductively coupled plasma mass spectrometry (ICP-MS)). In this evaluation, the agar gels showed an intrinsic capacity as sampler with respect to the gel Carbopol® and thus, the best option between the studied gels consisted on agar gels with 2 % of EDTA and the longest application time. On the whole, the agar gels showed an interesting potential as non-invasive samplers of built heritage deterioration materials which should be studied more in depth.

In the scope of the development of a microarray PhyloChip for the detection of toxic phytoplankton species, we designed a large series of probes specific against targets in the nuclear large subunit (LSU) rRNA of a range of Pseudo-nitzschia species and spotted these onto the microarray. Hybridisation with rRNA extracted from monoclonal cultures and from plankton samples revealed many cross-reactions. In the present work, we tested the functionality and specificity of 23 of these probes designed against ten of the species, using a dot-blot procedure. In this case, probe specificity is tested against the target region in PCR products of the LSU rRNA gene marker region blotted on nitrocellulose filters. Each filter was incubated with a species-specific oligoprobe. Eleven of the tested probes showed specific responses, identifying seven Pseudo-nitzschia species. The other probes showed non-specific responses or did not respond at all. Results of dot-blot hybridisations are more specific than those obtained with the microarray approach and the possible reasons for this are discussed.

Recent technical guidance has been published by the European Commission that outlines methodologies for the derivation of Environmental Quality Standards (EQS) in European surface waters under the Water Framework Directive (WFD). The guidance allows the derivation of a long-term EQS from a small dataset. Specifically an EQS can be derived from just three acute data points, although the safety factors built into such an EQS are large (e.g. up to a factor of 1,000). Large safety factors make such EQS uncertain, and often difficult to achieve in practice. We examine dataset requirements for the derivation of EQS and specifically the minimum number of tests needed for setting EQS for long-term chemical exposures that result in reduced relative uncertainty, as assessed simply through the reduction in standard deviation of the means of the values derived. Using ecotoxicity datasets for four example chemicals, for which EQS have been derived in many jurisdictions, we show that variation in the EQS is greatest when using the minimum dataset allowable under the WFD guidance, but decreases rapidly when seven or more datapoints are available. Increasing the minimum number of ecotoxicity data in deriving an EQS results in a greater understanding of ecotoxicological effects. With this knowledge, the mitigating effects of water chemistry can be accounted for in deriving an EQS, even with relatively limited datasets. The new guidance suggests “simplistic” approaches to account for chemical availability, but does not detail how this might be undertaken. We provide examples of ways by which water chemistry effects can be included in deriving implementable EQS for metals with relatively few reliable and relevant data.

This study considers the flux of radioactivity in flowback fluid from shale gas development in three areas: the Carboniferous, Bowland Shale, UK; the Silurian Shale, Poland; and the Carboniferous Barnett Shale, USA. The radioactive flux from these basins was estimated, given estimates of the number of wells developed or to be developed, the flowback volume per well and the concentration of K (potassium) and Ra (radium) in the flowback water. For comparative purposes, the range of concentration was itself considered within four scenarios for the concentration range of radioactive measured in each shale gas basin, the groundwater of the each shale gas basin, global groundwater and local surface water. The study found that (i) for the Barnett Shale and the Silurian Shale, Poland, the 1 % exceedance flux in flowback water was between seven and eight times that would be expected from local groundwater. However, for the Bowland Shale, UK, the 1 % exceedance flux (the flux that would only be expected to be exceeded 1 % of the time, i.e. a reasonable worst case scenario) in flowback water was 500 times that expected from local groundwater. (ii) In no scenario was the 1 % exceedance exposure greater than 1 mSv—the allowable annual exposure allowed for in the UK. (iii) The radioactive flux of per energy produced was lower for shale gas than for conventional oil and gas production, nuclear power production and electricity generated through burning coal.

A magnetic ZnFe₂O₄–reduced graphene oxide (rGO) hybrid was successfully developed as a heterogeneous catalyst for photo-Fenton-like decolorization of various dyes using peroxymonosulfate (PMS) as an oxidant under visible light irradiation. Through an in situ chemical deposition and reduction, ZnFe₂O₄nanoparticles (NPs) with an average size of 23.7 nm were anchored uniformly on rGO sheets to form a ZnFe₂O₄–rGO hybrid. The catalytic activities in oxidative decomposition of organic dyes were evaluated. The reaction kinetics, effect of ion species and strength, catalytic stability, degradation mechanism, as well as the roles of ZnFe₂O₄and graphene were also studied. ZnFe₂O₄–rGO showed to be a promising photocatalyst with magnetism for the oxidative degradation of aqueous organic pollutants and simple separation. The combination of ZnFe₂O₄NPs with graphene sheets leads to a much higher catalytic activity than pure ZnFe₂O₄. Graphene acted as not only a support and stabilizer for ZnFe₂O₄to prevent them from aggregation, largely improving the charge separation in the hybrid material, but also a catalyst for activating PMS to produce sulfate radicals at the same time. The ZnFe₂O₄–rGO hybrid exhibited stable performance without losing activity after five successive runs.

In this study, thermal desorption was combined with the addition of nano zerovalent iron (nZVI) to remediate polychlorinated biphenyl (PCB)-contaminated soil collected from a storage point for PCB-contaminated capacitors and transformers. The thermal desorption test conditions were varied from 300 to 600 °C, both with blank soil and with 100 mg of nZVI added. Next, the effect of the amount of nZVI added (0, 20, 40, 100, 200 mg) was investigated by thermal treatment at 400 °C. The test results show that thermal desorption eliminates most of the PCB load and that the presence of nZVI clearly enhances thermal desorption. After thermal treatment at 400 °C, a removal efficiency of 94.2 % was reached, with the use of 200 mg of nZVI. At 600 °C, the PCB removal efficiency after 1 h attained 98.35 % with 100 mg of nZVI and 97.40 % without nZVI. The presence of nZVI effectively decreased both the sum and the WHO-TEQ value of the 12 dl-PCBs.

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⁻¹dry weight (d.w.)) and in beach sand samples (0.69 ng g⁻¹d.w.) was an order of magnitude lower than in the styrofoam debris (5.20 ng g⁻¹d.w.). The highest mercury content observed in styrofoam debris (3,863 ng g⁻¹d.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.

A proposal for scaling-up the photocatalytic reactors is described and applied to the coated catalytic walls with a thin layer of titanium dioxide under the near ultraviolet (UV) irradiation. In this context, the photocatalytic degradation of isovaleraldehyde in gas phase is studied. In fact, the removal capacity is compared at different continuous reactors: a photocatalytic cylindrical reactor, planar reactor, and pilot unit. Results show that laboratory results can be useful for reactor design and scale-up. The flowrate increases lead to the removal capacity increases also. For example, with pilot unit, when flowrate extends four times, the degradation rate varies from 0.14 to 0.38 g h⁻¹ mcₐₜ ⁻². The influence of UV intensity is also studied. When this parameter increases, zboth degradation rate and overall mineralization are enhanced. Moreover, the effects of inlet concentration, flowrate, geometries, and size of reactors on the removal capacity are also studied.

Heavy metal contamination of soil resulting from treated wastewater irrigation can cause serious concerns resulting from consuming contaminated crops. Therefore, it is crucial to assess hazard related to wastewater reuse. In the present investigation, we suggest the use of biomarker approach as a new tool for risk assessment of wastewater reuse in irrigation as an improvement to the conventional detection of physicochemical accumulation in irrigated sites. A field study was conducted at two major sites irrigated with treated wastewater and comparisons were made with a control site. Different soil depths were considered to investigate the extent of heavy metal leaching, the estrogenic activity, and the biomarker response. Results have shown that a longer irrigation period (20 years) caused a slight decrease in soil metal levels when compared to the soil irrigated for 12 years. The highest levels of Cr, Co, Ni, Pb, and Zn were detected at 20 and 40 cm horizons in plots irrigated with wastewater for 12 years. The latter finding could be attributed to chemical leaching to deeper plots for longer irrigation period. Furthermore, the treated wastewater sample showed a high estrogenic activity while none of the soil samples could induce any estrogenic activity. Regarding the stress response, it was observed that the highest stress shown by the HSP47 promoter transfected cells was induced by a longer irrigation period. Finally, the treated wastewater and the irrigated soils exhibited an overexpression of HSP60 in comparison with reference soil following 1 h exposure. In conclusion, in vitro techniques can be efficiently used to assess potential hazard related to wastewater reuse.