Application of chemical oxidation to remediate HCH-contaminated soil under batch and flow through conditions

This is the first study describing the chemical oxidation of hexachlorocyclohexanes (HCHs) in contaminated soil under water saturated and unsaturated flow through conditions. Soil contaminated with β-HCH (45 mg kg^?1) and γ-HCH (lindane, 25 mg kg^?1) was sampled from former lindane waste storage site. Efficiency of following treatments was tested at circumneutral pH: H₂O₂ alone, H₂O₂/Fe^II, Na₂S₂O₈ alone, Na₂S₂O₈/Fe^II, and KMnO₄. Experimental conditions (oxidant dose, liquid/solid ratio, and soil granulometry) were first optimized in batch experiments. Obtained results revealed that increasing dose of H₂O₂ improved the oxidation efficiency while in Na₂S₂O₈ system, maximum HCHs were removed at 300 mM. However, oxidation efficiency was slightly improved by Fe^II-activation. Increasing the solid/liquid ratio decreased HCH removal in soil samples crushed to 500 μm while an opposite trend was observed for 2-mm samples. Dynamic column experiments showed that oxidation efficiency followed the order KMnO₄ > Na₂S₂O₈/Fe^II > Na₂S₂O₈ whatever the flow condition, whereas the removal extent declined at higher flow rate (e.g., ~50% by KMnO₄ at 0.5 mL/min as compared to ~30% at 2 mL/min). Both HCH removal and oxidant decomposition extents were found higher in saturated columns than the unsaturated ones. While no significant change in relative abundance of soil mineral constituents was observed before and after chemical oxidation, more than 60% of extractable organic matter was lost after chemical oxidation, thereby underscoring the non-selective behavior of chemical oxidation in soil. Due to the complexity of soil system, chemical oxidation has rarely been reported under flow through conditions, and therefore our findings will have promising implications in developing remediation techniques under dynamic conditions closer to field applications.     

Removal of heavy metal ions from wastewaters using dendrimer-functionalized multi-walled carbon nanotubes

Dendrimer-functionalized multi-walled carbon nanotubes (MWCNT) for heavy metal ion removal from wastewaters were developed. Triazole dendrimers (TD) were built directly onto the carbon nanotube surface by successive click chemistry reactions affording the zero- and first-generation dendrimer-functionalized MWCNT (MWCNT-TD1 and MWCNT-TD2). The Moedritzer-Irani reaction carried out on the amino groups present on the MWCNT-TD2 sample gave the corresponding α-aminophosphonate nanosystem MWCNT-TD2P. Both MWCNT-TD2 and MWCNT-TD2P nanosystems have been characterized by physical, chemical, and morphological analyses. Their chelating abilities towards the toxic metal ions Pb²⁺, Hg²⁺, and Ni²⁺ and the harmless Ca²⁺ ion have been experimentally evaluated in the two different sets of experiments and at the salt concentrations of 1 mg/mL or 1 μg/mL by inductively coupled plasma mass spectrometry (ICP-MS). The results of these studies pointed out the interesting chelating behavior for the phosphonated nanosystem towards the Hg²⁺ ion. The complexation mode of the best chelating system MWCNT-TD2P with mercury was investigated through density functional theory (DFT) calculations, suggesting a chelation mechanism involving the two oxygen atoms of the phosphate group. The synthesized dendrimers, supported on the multi-walled carbon nanotubes, have shown the potential to be used for the selective toxic metal ion removal and recovery.     

Dynamic of submicrometer particles in urban environment

Many studies show that particle toxicity increases with decreasing their size, emphasizing the role of submicrometric particles, in particular of ultrafine particles (<100 nm). In fact, particles greater than 2.5 μm are quickly removed through dry and wet deposition on the timescale of hours whereas submicrometer particles may reside in atmosphere for weeks, penetrate in indoor environment, and be long-range transported. High aerosol size resolution measurements are important for a correct assessment of the deposition efficiency in the human respiratory system, and time resolution is another important requisite. Starting from such considerations, time-resolved aerosol particle number size distributions have been measured in downtown Rome. Fast Mobility Particle Sizer (FMPS) and Scanning Mobility Particle Sizer (SMPS) measurements have been carried out at the INAIL’s Pilot Station, located in downtown Rome, in an area characterized by high density of autovehicular traffic. The two instruments have allowed to investigate deeply the urban aerosol in the range of 5.6–560 and 3.5–117 nm, respectively. In particular, the FMPS measurements have confirmed the interpretation about the transition phenomena in the time interval of few seconds, timescale typically associated with the emission of gasoline and diesel engines. In downtown Rome, the hourly average size distribution is bimodal or trimodal with maxima at about 5–15, 20–30, and 70–100 nm. Particle formation in the nucleation mode was associated to freshly emitted autovehicular exhaust.     

Insights into aqueous carbofuran removal by modified and non-modified rice husk biochars

Biochar has been considered as a potential sorbent for removal of frequently detected pesticides in water. In the present study, modified and non-modified rice husk biochars were used for aqueous carbofuran removal. Rice husk biochars were produced at 300, 500, and 700 °C in slow pyrolysis and further exposed to steam activation. Biochars were physicochemically characterized using proximate, ultimate, FTIR methods and used to examine equilibrium and dynamic adsorption of carbofuran. Increasing pyrolysis temperature led to a decrease of biochar yield and increase of porosity, surface area, and adsorption capacities which were further enhanced by steam activation. Carbofuran adsorption was pH-dependant, and the maximum (161 mg g^?1) occurred in the vicinity of pH 5, on steam-activated biochar produced at 700 °C. Freundlich model best fitted the sorption equilibrium data. Both chemisorption and physisorption interactions on heterogeneous adsorbent surface may involve in carbofuran adsorption. Langmuir kinetics could be applied to describe carbofuran adsorption in a fixed bed. A higher carbofuran volume was treated in a column bed by a steam-activated biochar versus non-activated biochars. Overall, steam-activated rice husk biochar can be highlighted as a promising low-cost sustainable material for aqueous carbofuran removal.     

Effective adsorbent for arsenic removal: core/shell structural nano zero-valent iron/manganese oxide

Recently, nano zero-valent iron (nZVI) has emerged as an effective adsorbent for the removal of arsenic from aqueous solutions. However, its use in various applications has suffered from reactivity loss resulting in a decreased efficiency. Thus, the aim of this study was to develop an effective arsenic adsorbent as a core/shell structural nZVI/manganese oxide (or nZVI/Mn oxide) to minimize the reactivity loss of the nZVI. As the major result, the arsenic adsorption capacities of the nZVI/Mn oxide for As(V) and As(III) were approximately two and three times higher than that of the nZVI, respectively. In addition, the As(V) removal efficiency of the nZVI/Mn oxide was maintained through 4 cycles of regeneration whereas that of the nZVI was decreased significantly. The enhanced reactivity and reusability of the nZVI/Mn oxide can be successfully explained by the synergistic interaction of the nZVI core and manganese oxide shell, in which the manganese oxides participate in oxidation reactions with corroded Fe²⁺ and subsequently retard the release of aqueous iron providing additional surface sites for arsenic adsorption. In summary, this study reports the successful fabrication of a core/shell nZVI/Mn oxide as an effective adsorbent for the removal of arsenic from aqueous solutions.     

Investigation of the accumulation of ash,heavy metals,and polycyclic aromatic hydrocarbons to assess the stability of lysis–cryptic growth sludge reduction in sequencing batch reactor

The accumulation of ash, heavy metals, and polycyclic aromatic hydrocarbons (collectively called potential accumulating substances, PAS) was evaluated to ascertain the stability of lysis–cryptic growth sludge reduction process (LSRP) for municipal sludge treatment. One sequencing batch reactor (SBR) incorporated with homogenization was run to test the LSRP and another SBR as a control. The continuous monitoring results for 2 months showed that the ash and heavy metals slightly increased, and the polycyclic aromatic hydrocarbons decreased by 18.0%, indicating that there may be negligible accumulations during the LSRP. Their accumulations met pattern I, as demonstrated by statistical analysis, proving no PAS accumulation for LSRP. This was further confirmed by sludge activity and system performance. Moreover, the mechanism for no PAS accumulation was discussed. It was concluded that the LSRP was stable with no worries about PAS accumulation under the operational conditions.     

Prediction of membrane fouling using artificial neural networks for wastewater treated by membrane bioreactor technologies: bottlenecks and possibilities

Membrane fouling is a major concern for the optimization of membrane bioreactor (MBR) technologies. Numerous studies have been led in the field of membrane fouling control in order to assess with precision the fouling mechanisms which affect membrane resistance to filtration, such as the wastewater characteristics, the mixed liquor constituents, or the operational conditions, for example. Worldwide applications of MBRs in wastewater treatment plants treating all kinds of influents require new methods to predict membrane fouling and thus optimize operating MBRs. That is why new models capable of simulating membrane fouling phenomenon were progressively developed, using mainly a mathematical or numerical approach. Faced with the limits of such models, artificial neural networks (ANNs) were progressively considered to predict membrane fouling in MBRs and showed great potential. This review summarizes fouling control methods used in MBRs and models built in order to predict membrane fouling. A critical study of the application of ANNs in the prediction of membrane fouling in MBRs was carried out with the aim of presenting the bottlenecks associated with this method and the possibilities for further investigation on the subject.     

Effect of acute exposure to PFOA on mouse liver cells in vivo and in vitro

Increasingly, epidemiological evidences indicate chemosynthetic perfluorooctanoic acid (PFOA), an environmental pollutant, induces potential adverse effect on human health after long-term exposure. However, less study has been performed for assessment of acute effect of PFOA exposure on metabolic homeostasis. In experimental designs, PFOA-exposed liver cells in vivo and in vitro were used to discuss underlying mechanism related to PFOA-induced metabolic dysfunction. In serological tests, PFOA-exposed mice showed increased treads of liver functional enzymes in alanine transaminase (ALT), aspartate transaminase (AST), and total bilirubin (T-BIL), trypsinase, low density lipoprotein-cholesterol (LDL-C), and insulin, while blood glucose, high density lipoprotein-cholesterol (HDL-C), and glucagon levels were reduced. In histocytological observations, PFOA-exposed liver showed visible cytoplasmic vesicles, and intact pancreatic islets were observed in PFOA-exposed pancreas. Additionally, increased insulin-positive cells and reduced glucagon-positive cells were detected in PFOA-exposed islets. As shown in immunoassays, PFOA-exposed liver resulted in elevations of cluster of differentiation 36 (CD36)-labeled cells and CD36 protein. In mouse liver cell study, PFOA-exposed cells showed increased cell apoptotic count, and increased phosphorylated levels of Bcl-2 and Bad in the cells. Furthermore, PFOA-exposed liver cells exhibited elevations of CD36-labeled cells and CD36 protein. Taken together, the present data demonstrate that acute exposure to PFOA-impaired liver function is associated with inducting CD36 expression and apoptosis, as well as disrupting key hormones in the pancreas.     

Bringing together raptor collections in Europe for contaminant research and monitoring in relation to chemicals regulations

Raptors are good sentinels of environmental contamination and there is good capability for raptor biomonitoring in Europe. Raptor biomonitoring can benefit from natural history museums (NHMs), environmental specimen banks (ESBs) and other collections (e.g. specialist raptor specimen collections). Europe’s NHMs, ESBs and other collections hold large numbers of raptor specimens and samples, covering long periods of time. These collections are potentially a valuable resource for contaminant studies over time and space. There are strong needs to monitor contaminants in the environment to support EU and national chemical management. However, data on raptor specimens in NHMs, ESBs and other collections are dispersed, few are digitised, and they are thus not easy to access. Specimen coverage is patchy in terms of species, space and time. Contaminant research with raptors would be facilitated by creating a framework to link relevant collections, digitising all collections, developing a searchable meta-database covering all existing collections, making them more visible and accessible for contaminant research. This would also help identify gaps in coverage and stimulate specimen collection to fill gaps in support of prioritised contaminant monitoring. Collections can further support raptor biomonitoring by making samples available for analysis on request.     

The use of ultrasound-assisted anaerobic compost tea washing to remove poly-chlorinated dibenzo-p-dioxins (PCDDs), dibenzo-furans (PCDFs) from highly contaminated field soils

The remediation of dioxin-contaminated soil of a specific coastal area previously employed for the manufacture of pentachlorophenol (PCP) in southern Taiwan’s Tainan City has attracted much attention of researchers there. This work addresses the possibility of providing an effective and environmentally friendly option for removing PCDD/Fs from soil in that field. Soil screening/sieving was first conducted to assess particle distribution. Fine sand was observed to be the major component of the soil, accounting for more than 60% of the total mass. A combination of ultrasonification and mechanical double-blade agitation was used to facilitate the washing of the soil using the biosurfactant anaerobic compost tea. More than 85 and 95% of total removal efficiencies were achieved for moderately and highly contaminated soils after 6 and 10 washing cycles, respectively, under ambient temperature, a soil/liquid ratio 1:2.5, 700 rpm, and over a relatively short duration. These results were achieved through the collision and penetration effects of this combined treatment as well as PCDD/F partitioning between the particles and anaerobic compost tea. This study represents the first to report the use of anaerobic compost tea solvent to wash soil highly contaminated by dioxin. It was concluded that anaerobic compost tea, rich in non-toxic bio-surfactants (e.g., alcohols, humic acids), can be used to improve bioavailability and bioactivity of the soil making bio-attenuation and full remediation more efficient.