Interactions of ciprofloxacin (CIP), titanium dioxide (TiO2) nanoparticles and natural organic matter (NOM) in aqueous suspensions.

The aim of the present study was to investigate interactions of the antibiotic ciprofloxacin (CIP), titanium dioxide nanoparticles (TiO2 NP) and natural organic matter (NOM) in aqueous suspensions. The mean hydrodynamic diameter of particles of TiO2 NP and NOM in the suspensions ranged from 113 to 255nm. During batch experiments the radioactivity resulting from (14)CIP was determined in the filtrate (filter pore size 100nm) by scintillation measurements. Up to 72h, no significant sorption of NOM to TiO2 NP was observed at a TiO2 NP concentration of 5mg/L. When the concentration of TiO2 NP was increased to 500mg/L, a small amount of NOM of 9.5%±0.6% was sorbed at 72h. The low sorption affinity of NOM on TiO2 NP surfaces could be explained by the negative charge of both components in alkaline media or by the low hydrophobicity of the NOM contents. At a TiO2 NP concentration of 5mgL(-1), the sorption of CIP on TiO2 NP was insignificant (TiO2 NP/CIP ratio: 10). When the TiO2 NP/CIP ratio was increased to 1000, a significant amount of 53.6%±7.2% of CIP was sorbed on TiO2 NP under equilibrium conditions at 64h. In alkaline media, CIP is present mainly as zwitterions which have an affinity to sorb on negatively charged TiO2 NP surfaces. The sorption of CIP on TiO2 NP in the range of TiO2 NP concentrations currently estimated for municipal wastewater treatment plants is estimated to be rather low. The Freundlich sorption coefficients (KF) in the presence of NOM of 2167L(n)mgmg(-n)kg(-1) was about 10 times lower than in the absence of NOM. This is an indication that the particle fraction of NOM<100nm could play a role as a carrier for ionic organic micro-pollutants as CIP.

Precipitation of arsenic sulphide from acidic water in a fixed-film bioreactor.

Arsenic (As) is a toxic element frequently present in acid mine waters and effluents. Precipitation of trivalent arsenic sulphide in sulphate-reducing conditions at low pH has been studied with the aim of removing this hazardous element in a waste product with high As content. To achieve this, a 400m L fixed-film column bioreactor was fed continuously with a synthetic solution containing 100mg L(-1) As(V), glycerol and/or hydrogen, at pH values between 2.7 and 5. The highest global As removal rate obtained during these experiments was close to 2.5mg L(-1)h(-1). A switch from glycerol to hydrogen when the biofilm was mature induced an abrupt increase in the sulphate-reducing activity, resulting in a dramatic mobilisation of arsenic due to the formation of soluble thioarsenic complexes. A new analytical method, based on ionic chromatography, was used to evaluate the proportion of As present as thioarsenic complexes in the bioreactor. Profiles of pH, total As and sulphate concentrations suggest that As removal efficiency was linked to solubility of orpiment (As(2)S(3)) depending on pH conditions. Molecular fingerprints revealed fairly homogeneous bacterial colonisation throughout the reactor. The bacterial community was diverse and included fermenting bacteria and Desulfosporosinus-like sulphate-reducing bacteria. arrA genes, involved in dissimilatory reduction of As(V), were found and the retrieved sequences suggested that As(V) was reduced by a Desulfosporosinus-like organism. This study was the first to show that As can be removed by bioprecipitation of orpiment from acidic solution containing up to 100mg L(-1) As(V) in a bioreactor.

Influence of montmorillonite tactoid size on Na-Ca cation exchange reactions.

The spatial organisation of swelling clay platelets in a suspension depends on the chemical composition of the equilibration solution. Individual clay platelets can be well dispersed, with surfaces entirely in contact with the external solution, or be stacked in tactoids, where part of the surfaces forms parallel alignments embedding interlayer water and cations. External and interlayer surfaces do not exhibit similar affinities for cations having different hydration and charge properties and the clay platelet stacking arrangement influences the clay affinity for these cations. This paper aims to establish the link between exchange properties and clay tactoid size and organisation for Na-Ca exchange on montmorillonite. Different montmorillonite samples behave differently with regards to Na-Ca exchange, from ideal to non-ideal exchange behaviour. A simple model coupling the tactoid stacking size to different Na/Ca relative affinities of the external and interlayer clay surfaces enables these differences to be reproduced.

Metal speciation in landfill leachates with a focus on the influence of organic matter.

This study characterises the heavy-metal content in leachates collected from eight landfills in France. In order to identify heavy metal occurrence in the different size fractions of leachates, a cascade filtration protocol was applied directly in the field, under a nitrogen gas atmosphere to avoid metal oxidation. The results of analyses performed on the leachates suggest that most of the metals are concentrated in the <30 kDa fraction, while lead, copper and cadmium show an association with larger particles. Initial speciation calculations, without considering metal association with organic matter, suggest that leachate concentrations in lead, copper, nickel and zinc are super-saturated with respect to sulphur phases. Speciation calculations that account for metal complexation with organic matter, considered as fulvic acids based on C1(s) NEXAFS spectroscopy, show that this mechanism is not sufficient to explain such deviation from equilibrium conditions. It is therefore hypothesized that the deviation results also from the influence of biological activity on the kinetics of mineral phase precipitation and dissolution, thus providing a dynamic system. The results of chemical analyses of sampled fluids are compared with speciation calculations and some implications for the assessment of metal mobility and natural attenuation in a context of landfill risk assessment are discussed.

Environmental impacts of unmanaged solid waste at a former base metal mining and ore processing site (Kirki, Greece).

The Kirki project aimed to identify, among the mining waste abandoned at a mine and processing plant, the most critical potential pollution sources, the exposed milieus and the main pathways for contamination of a littoral area. This was accompanied by the definition of a monitoring network and remedial options. For this purpose, field analytical methods were extensively used to allow a more precise identification of the source, to draw relevant conceptual models and outline a monitoring network. Data interpretation was based on temporal series and on a geographical model. A classification method for mining waste was established, based on data on pollutant contents and emissions, and their long-term pollution potential. Mining waste present at the Kirki mine and plant sites comprises (A) extraction waste, mainly metal sulfide-rich rocks; (B) processing waste, mainly tailings, with iron and sulfides, sulfates or other species, plus residues of processing reagents; and (C) other waste, comprising leftover processing reagents and Pb-Zn concentrates. Critical toxic species include cadmium and cyanide. The stormy rainfall regime and hilly topography favour the flush release of large amounts of pollutants. The potential impacts and remedial options vary greatly. Type C waste may generate immediate and severe chemical hazards, and should be dealt with urgently by careful removal, as it is localised in a few spots. Type B waste has significant acid mine drainage potential and contains significant amounts of bioavailable heavy metals and metalloids, but they may also be released in solid form into the surface water through dam failure. The most urgent action is thus dams consolidation. Type A waste is by far the most bulky, and it cannot be economically removed. Unfortunately, it is also the most prone to acid mine drainage (seepage pH 1 to 2). This requires neutralisation to prevent acid water accelerating heavy metals and metalloids transfer. All waste management options require the implementation of a monitoring network for the design of a remediation plan, efficiency control, and later, community alert in case of accidental failure of mitigation/remediation measures. A network design strategy based on field measurements, laboratory validation and conceptual models is proposed.

Reactivity of waste generated during lead recycling: an integrated study.

Lead consumption in Europe is 2.054 M tonnes/year, more than 70% of which is produced by recycling and, more specifically, the recycling of car batteries. This industry is jeopardised by the method employed so far, recycling by alkaline fusion, because the treatment produces 200,000 tonnes of toxic and unstable slag. The study presented here attempts to clarify the approach and the combined tools employed (mineralogy, chemistry, leaching, thermodynamics), to construct a coherent physicochemical model of slag behaviour. The model was then used to carry out sensitivity analyses with various landfill scenarios, and to propose adjustments to the process to recover the residual heavy metals and to upgrade as secondary raw products the co-products generated by the inerting of the slag.