Nontargeted evaluation of the fate of steroids during wastewater treatment by comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry

Emerging organic contaminants in wastewater are usually analyzed by targeted approaches, and especially estrogens have been the focus of environmental research due to their high hormonal activity. The selection of specific target compounds means, however, that most of the sample components, including transformation products and potential new contaminants, are neglected. In this study, the fate of steroidal compounds in wastewater treatment processes was evaluated by a nontargeted approach based on comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry. The potential of the nontargeted approach to generate comprehensive information about sample constituents was demonstrated with use of statistical tools. Transformation pathways of the tentatively identified compounds with steroidal four-ring structure were proposed. The purification efficiency of the wastewater treatment plants was studied, and the distribution of the compounds of interest in the suspended solids, effluent water, and sludge was measured. The results showed that, owing to strong adsorption of hydrophobic compounds onto the solid matter, the steroids were mostly bound to the suspended solids of the effluent water and the sewage sludge at the end of the treatment process. The most abundant steroid class was androstanes in the aqueous phase and cholestanes in the solid phase. 17β-estradiol was the most abundant estrogen in the aqueous phase, but it was only detected in the influent samples indicating efficient removal during the treatment process. In the sludge samples, however, high concentrations of an oxidation product of 17β-estradiol, estrone, were measured.     

Electrochemical wastewater treatment: influence of the type of carbon and of nitrogen on the organic load removal

Boron-doped diamond (BDD) and Ti/Pt/PbO₂ anodes were utilized to perform the electrodegradation of synthetic samples containing humic acid in the presence of different organic and inorganic carbon-containing and nitrogen-containing compounds. The influence of the chloride ion in the degradation process of the different synthetic samples was also assessed. The results showed that the anodic oxidation process can efficiently degrade recalcitrant compounds such as humic acid. The presence of carbonate in solution enhances the nitrogen removal, whereas it hinders the oxidation of the organic compounds. When organic nitrogen is present, it is converted to NH₄ ⁺, which in turn is oxidized to nitrate and to volatile nitrogen compounds. Hydroxyl radicals are more prone to oxidize the organic nitrogen than the ammonium nitrogen. The presence of chloride enhances the organic matter and nitrogen removal rates, BDD being the anode material that yields the highest removals.     

Lead contamination of the Seine River, France: geochemical implications of a historical perspective

Four sediment cores collected in the Seine River basin and dated between 1916 and 2003 were analyzed for lead concentrations and isotopic composition. In all four cores, the measured Pb concentration (up to 460 mg kg⁻¹) lies significantly above the natural background (27-40 mg kg⁻¹), although a significant decrease (down to 75 mg kg⁻¹) was observed during the second half of the 20th century which can be explained by the reduction of lead emissions. The ²⁰⁶Pb/²⁰⁷Pb ratio measured in these samples indicates that the main source of Pb used in the Paris conurbation is characterized by a “Rio Tinto” signature (defined as ²⁰⁶Pb/²⁰⁷Pb = 1.1634 ± 0.0001). A high contribution, up to 25%, from the leaded gasoline (characterized by ²⁰⁶Pb/²⁰⁷Pb = 1.08 ± 0.02) is revealed in the Seine River downstream Paris, indicating that lead from the leaded gasoline is preferentially released to the river.The dominating Pb signature in the Paris conurbation that is currently sampled through incinerators fumes (²⁰⁶Pb/²⁰⁷Pb = 1.1550 ± 0.0005) and waste water treatment plant (²⁰⁶Pb/²⁰⁷Pb = 1.154 ± 0.002), represents a mixture of highly recycled lead from the Rio Tinto mine and lead from leaded gasoline (imprinted by the low ²⁰⁶Pb/²⁰⁷Pb of the Broken Hill mine). This signature is called “urban” rather than “industrial”, because it is clearly distinct from the Pb that is found in areas contaminated by heavy industry, i.e. the heavy industries located on the Oise River which used lead from European ores characterized by high ²⁰⁶Pb/²⁰⁷Pb ratios (∼1.18-1.19) and possibly a minor amount of North American lead (²⁰⁶Pb/²⁰⁷Pb ratios > 1.20). The “urban” signature is also found in a rural area upstream of Paris in the 1970’s. At the Seine River mouth in 2003, Pb with an urban signature represents 70% of the total Pb sediment content, with the 30% remaining corresponding to natural Pb.     

Comparative bioaccumulation kinetics of trace elements in Mediterranean marine sponges

While marine organisms such as bivalves, seagrasses and macroalgae are commonly used as biomonitors for the environment pollution assessment, widely distributed sponges received little attention as potential helpful species for monitoring programmes. In this study, the trace element and radionuclide bioaccumulation and retention capacities of some marine sponges were estimated in a species-comparative study using radiotracers technique. Six Mediterranean species were exposed to background dissolved concentrations of ^110mAg, ²⁴¹Am, ¹⁰⁹Cd, ⁶⁰Co, ¹³⁴Cs, ⁵⁴Mn, ⁷⁵Se and ⁶⁵Zn allowing the assessment of the uptake and depuration kinetics for selected elements. Globally, massive demosponges Agelas oroides, Chondrosia reniformis and Ircinia variabilis displayed higher concentration factor (CF) than the erectile ones (Acanthella acuta, Cymbaxinella damicornis, Cymbaxinella verrucosa) at the end of exposure, suggesting that the morphology is a key factor in the metal bioaccumulation efficiency. Considering this observation, two exceptions were noted: (1) A. acuta reached the highest CF for ^110mAg and strongly retained the accumulated metal without significant Ag loss when placed in depuration conditions and (2) C. reniformis did not accumulate Se as much as A. oroides and I. variabilis. These results suggest that peculiar metal uptake properties in sponges could be driven by specific metabolites or contrasting biosilification processes between species, respectively. This study demonstrated that sponges could be considered as valuable candidate for biomonitoring metal contamination but also that there is a need to experimentally highlight metal-dependant characteristic among species.     

Degradation of carbofuran and carbofuran-derivatives in presence of humic substances under basic conditions

The influence of humic aggregates in water solution upon the chemical stability of carbofuran (CF) and the carbofuran-derivatives, 3-hydroxy-carbofuran (HCF) and 3-keto-carbofuran (KCF), has been investigated in basic media. An inhibition upon the basic hydrolysis of 3-hydroxy-carbofuran and 3-keto-carbofuran (∼1.7 and ∼1.5-fold, respectively) was observed and it was rationalized in terms of the micellar pseudophase model. Nevertheless, non-significant effect upon the carbofuran stability was found in the presence of humic substances. These behaviors have been compared with the corresponding ones in other synthetic colloidal aggregates.     

Toxicity of silver nanoparticles to rainbow trout: A toxicogenomic approach

Silver (Ag) nanoparticles are used as antimicrobial adjuvant in various products such as clothes and medical devices where the release of nano-Ag could contaminate the environment and harm wildlife. The purpose of this study was to examine the sublethal effects of nano-Ag and dissolved Ag on Oncorhynchus mykiss rainbow trout. Hepatic Ag contents and changes in gene expression were monitored to provide insights on bioavailability and mode of action of both forms of silver. Fish were exposed to increasing concentrations (0.06, 0.6 and 6 μg L⁻¹) of nano-Ag (20 nm) and silver nitrate (AgNO₃) for 96 h at 15 °C. A gene expression analysis was performed in the liver using a DNA microarray of 207 stress-related genes followed by a quantitative polymerase chain reaction on a selection of genes for validation. The biochemical markers consisted of the determination of labile zinc, metallothioneins, DNA strand breaks, lipid peroxidation (LPO) and vitellogenin-like proteins. The analysis of total Ag in the aquarium water revealed that nano-Ag was mostly aggregated, with 1% of the total Ag being dissolved. Nevertheless, hepatic Ag content was significantly increased in exposed fish. Indeed, dissolved Ag was significantly more bioavailable than nano-Ag only at the highest concentration with 38 ± 10 and 11 ± 3 ng Ag mg⁻¹ proteins for dissolved and nano-Ag respectively. Exposure to both forms of Ag led to significant changes in gene expression for 13% of tested gene targets. About 12% of genes responded specifically to nano-Ag, while 10% of total gene targets responded specifically to dissolved Ag. The levels of vitellogenin-like proteins and DNA strand breaks were significantly reduced by both forms of Ag, but DNA break levels were lower with nano-Ag and could not be explained by the presence of ionic Ag. Labile zinc and the oxidized fraction of metallothioneins were increased by both forms of Ag, but LPO was significantly induced by nano-Ag only. A discriminant function analysis revealed that the responses obtained by biochemical markers and a selection of ten target genes were able to discriminate completely (100%) the effects of both forms of Ag. Exposure to nano-Ag involved genes in inflammation and dissolved Ag involved oxidative stress and protein stability. Hence, the toxicity of Ag will differ depending on the presence of Ag nanoparticles and aggregates.     

Blood Pb and δ-ALAD inhibition in cattle and sheep from a Pb-polluted mining area

The effects of Pb pollution on cattle and sheep raised in an ancient mining area were studied through the use of blood Pb (PbB) levels and δ-aminolevulinic acid dehydratase (δ-ALAD) activity. Lead levels in livestock blood from the mining area (n=110) were significantly elevated when compared to the controls (n=79). In 91.4% of cattle (n=58) and 13.5% of sheep (n=52) sampled in the mining area, PbB levels corresponded to subclinical exposure (6-35 μg/dl). Two young cattle (<2 years) from the mining area (n=5) had PbB levels indicative of clinical poisoning (>35 μg/dl). Elevated PbB was also accompanied by δ-ALAD activity inhibition in blood, which confirms that measurable effects of Pb poisoning were taking place. Observed PbB levels suggest that a potential risk to human consumers of beef from the Pb polluted areas may also exist, as has been shown previously for game meat from the same mining area.     

Gene expression of heat shock protein 70, interleukin-1β and tumor necrosis factor α as tools to identify immunotoxic effects on Xenopus laevis: a dose-response study with benzo[a]pyrene and its degradation products

The exposure to benzo[a]pyrene (B[a]P) results in an alteration of immune function in mammals and fish, and the analysis of cytokine mRNA levels has been suggested for predicting the immunomodulatory potential of chemicals. To obtain evidence of the innate immune responses to B[a]P in Xenopus laevis, the present study monitored the mRNA expression of interleukin 1-β (IL-1β), tumor necrosis factor α (TNF-α) and heat shock protein 70 (HSP70) in a laboratorial exposure. Tadpoles exposed to 8.36, 14.64, 89.06 and 309.47 μg/L of B[a]P,were used for detecting hsp70, IL-1β and TNF-α mRNA induction. A dose-response increase in the expression of hsp70 and IL-1β mRNA was found. The results of this study confirmed the use of hsp70 and IL-1β, but not TNF-α, as sensitive indicators of immunotoxic effect of B[a]P in X. laevis. Further research would be required for the validation of these endpoints.