Seven phthalate by-products were investigated for the first time, in target tissues of roach from a contaminated river of the Ile-de-France district. All parent phthalates were bioaccumulated in liver and muscle and liver contents were correlated with river concentrations (p < 0.01). All metabolites were found in liver, plasma and bile. The mono-iso-butyl phthalate (MiBP; 1.6 μg g⁻¹dw of liver), followed by mono-n-butyl phthalate (MnBP; 1.5 μg g⁻¹dw of liver) were the most abundant ones. Among the three metabolites of di-ethylhexyl phthalate (DEHP), mono (2-ethylhexyl) phthalate (MEHP) predominated in bile (15.5 ng ml⁻¹) and liver (0.237 μg g⁻¹dw), whereas in plasma, it was mono (2-ethyl-5-hydroxyhexyl) phthalate – MEHHP (214 ng ml⁻¹). In liver, MEHP/DEHP ratios ranged from 0.04 to 0.2. Among the oxidized metabolites, only mono (2-ethyl-5-oxohexyl) phthalate (MEOHP) was correlated (p < 0.05) with parent DEHP and appeared to be a more reliable marker of DEHP impact than the monoester.

Mercury (Hg) concentrations in muscles of wild alligators (Melanosuchus niger) from the Mamirauá Reservoir (a reference area in the Brazilian Amazon) and the human health risks associated with its consumption were assessed. The mean Hg concentration in alligator muscles was 0.407 ± 0.114 μg/g (N = 61). Close to 5 % of the muscle samples showed Hg levels above the World Health Organization guideline for fish consumption (0.5 μg/g). A positive and significant relationship was observed between Hg concentrations in muscle and the age of the specimens. The dose-response approach suggests that close to 27.4 years is required for half of the exposed specimens to attain 0.5 μg/g. The hazard quotient (HQ) is a risk indicator which defines the ratio of exposure level and a toxicological reference dose. HQ resulted above the unity for all the specimens when the ingestion rate for riverine communities (200 g of muscle per day) is considered, indicating the existence of hazard. When the ingestion rate for market consumers (28.57 g/day) is considered, the risks are much lower (mean HQ = 0.55), suggesting that such group is not at risk. The establishment of local and regional ingestion rates for riverine populations and market consumers is extremely recommended.

Reusing sewage sludge as a soil fertiliser has become a common alternative to disposal. Although this practice has a few benefits, it may contribute to the medium- and long-term contamination of the trophic chain because sewage sludge may contain heavy metals and organic contaminants. As the leaching of contaminants may depend on the sludge pre-treatment, the leaching of heavy metals (Cu, Ni, Pb, Zn and Cr) and alkylphenolic compounds (APCs) (octylphenol (OP), nonylphenol (NP), nonylphenol-mono-ethoxylate (NP₁EO)) was investigated in five fresh and 40 °C dried sewage sludge samples from north-eastern Spain. FT-IR analyses and full-scan GC-MS chromatograms showed that sludge drying changed the nature of organic compounds leading to changes in their solubility. Moreover, sludge drying led to a higher relative contribution of dissolved organic carbon than the particulate organic carbon in the leachates. Leaching of Pb, Zn and Cr was below 5 % in both fresh and dried sludge samples, whereas Cu and Ni leached at rates up to 12 and 43 %, respectively, in some of the dried sludge samples. The leaching yields of OP, NP and NP₁EO ranged from 1.3 to 35 % for fresh samples, but they decreased from 0.8 to 3.4 % in dried samples. The decrease in the leachability of APCs observed in dried sludge samples might be attributed to the fact that these compounds are associated with particulate organic matter, with significantly lower concentration or even absent in dried sludge than in fresh sludge samples. Therefore, it is recommended to dry the sludge before its disposal.

In the present work, the coupling of adsorption and electrochemical oxidation on a boron-doped diamond (BDD) electrode to treat solutions containing dyes is studied. This coupling may be convenient for the treatment of diluted pollutant that is limited by the low rate of electrooxidation due to mass-transfer limitation. A pre-concentration step by adsorption could minimize the design of the electrochemical reactor. The adsorbent chosen was mixed with softwood sawdust, and methylene blue was chosen as the model dye molecule. Isotherms of adsorption and kinetics were investigated as well as the effects of current density and regeneration time. The BDD electrochemical oxidation of methylene blue adsorbed onto sawdust led simultaneously to its degradation and sawdust regeneration for the next adsorption. It was observed that multiple adsorption and electrochemical regeneration cycles led to an enhancement of adsorption capacity of the sawdust. This study demonstrated that adsorption–electrochemical degradation coupling offers a promising approach for the efficient elimination of organic dyes from wastewater.

Environmental characteristics in water and sediments of two contrasted coastal Mediterranean lagoons, Bages-Sigean and Canet-St Nazaire, were measured over a three season survey. The urban pollution (treatment plant discharges) is very important in Canet-St Nazaire lagoon reflecting untreated sewages, while in Bages-Sigean, the northern part appears more impacted due to larger anthropogenic inputs. Dissolved Cd concentrations are on the whole similar in both lagoons, whereas Cu concentrations are by far higher in lagoon Canet-St Nazaire. Cu concentrations appear to be highly dependent on dissolved organic carbon whereas salinity seems to control Cd variations. Concerning the sediments, the confined northern part of lagoon Bages-Sigean shows organic carbon and total nitrogen enrichment whereas lipid concentrations are much higher in the Canet-St Nazaire lagoon. Cu complexation seems to be strongly related to organic matter as evidenced by the two significant positive relationships, on one hand between Cu and organic carbon, and on the other hand, between Cu and lipids. On the contrary, Cd concentrations appear to be mainly controlled by carbonates. PCBs and PBDEs were detected only in sediments and show relatively low concentrations compared to similar lagoon environments. Regarding the sediment quality guidelines, Cd, Cu and PCBs in both lagoons did not exceed any Probable Effect Concentration (PEC).

Korean water quality managers are required to promptly develop national assessment standards for freshwater sediment quality due to the Four Major River Restoration Project in Korea in 2009. We conducted this study to develop sediment management standards (SMSs), determining obviously and severely polluted sediment, which could have adverse impacts on water quality and aquatic ecosystem. The SMSs values were derived from the 95th percentile of concentration distribution for organic matter and nutrients in sediment quality database. For the SMSs of metals, foreign sediment quality guidelines (SQGs) were adopted. As a result, 13 % for loss on ignition (LOI), 1,600 mg/kg for total phosphorus (TP), and 5,600 mg/kg for total nitrogen (TN) were set as the SMSs for freshwater sediment in Korea. These values were higher than the range of heavily polluted sediment from USEPA Region 5 guideline derived by the similar approaches for the Great Lakes harbor sediments, and similar or lower than the severe effect level (SEL) from provincial sediment quality guideline (PSQG) of Ontario, Canada by screening level concentration (SLC) approach. However, SMSs in the present study are appropriate considering the concentration ranges and the Korean SMSs’ definition for freshwater sediments in Korea. The Puget Sound marine sediment cleanup screening level (CSL) in Washington State, USA were adopted as the Korean SMSs for As (93 mg/kg), Cd (6.7 mg/kg), Cr (270 mg/kg), Cu (390 mg/kg), Pb (530 mg/kg), and Zn (960 mg/kg) in freshwater sediments. Hg concentration (0.59 mg/kg) of CSL was too low to determine the polluted freshwater sediments in Korea, and the SEL of Ontario, Canada for mercury concentration (2 mg/kg) was selected as the SMS for Hg. These values were found reasonable through the assessment of applicability with the datasets from locations directly affected by obvious point sources. These results indicate that SMSs for organic matter, nutrient, and metals derived within the present study can successfully determine obviously and severely polluted sediment in Korea. However, the SMSs have limits to specifically determine the effects of polluted sediment on water quality and aquatic ecosystem in Korea. Thus, we will revise and specify SMSs considering those effects and further sediment quality assessment framework in the near future.

Battery tests serve as integral tools to decide whether a treatment process is ecotoxicologically safe or not. In the present study, a battery of toxicity tests was employed to elucidate the toxicity of the potential endocrine-disrupting pollutant bisphenol A (BPA) and its advanced oxidation products. For this purpose, BPA was subjected to Fenton treatment in the growth medium of the test organisms employed as well as in real lake water. Treatment results indicated that BPA removals were fast and complete within less than a minute, whereas total organic carbon (TOC) removals were rather incomplete, speaking for the accumulation of refractory degradation products. The presence of chloride and/or natural organic matter influenced H₂O₂ consumption rates and the treatment performance of the Fenton’s reagent as well. The sensitivity of the selected test organisms for BPA and its Fenton treatment products in different water matrices was found in the following decreasing order: the freshwater microalgae (Pseudokirchneriella subcapitata) > the freshwater cladoceran (Daphnia magna) > marine photobacteria (Vibrio fischeri).

Chronic exposure to heavy metals has long been recognized as being capable of increasing head and neck cancer (HNC) incidence, such as laryngeal (LC) and nasopharyngeal (NPC), among exposed human populations. The aim of the present study was to evaluate the concentrations of arsenic (As) and cadmium (Cd) in the blood of 145 patients (LC and NPC) and 351 controls in order to establish a potential relationship between these factors and the occurrence of LC and NPC. Mean blood levels of As and Cd in patients (5.67 and 3.51 μg/L, respectively) were significantly higher than those of controls (1.57 and 0.74 μg/L, respectively). The blood levels of As and Cd were mostly significantly higher than those of controls (p < 0.05) after controlling the other risk factors of HNC including tobacco smoking and chewing, and alcohol drinking. Cd levels in blood increase significantly with the number of occupational exposure years for patients (p < 0.05). However, seafood was not found to be contributing as an exposure source. Among these risk factors, smoking (>30 pack years) and occupational exposure (>20 years) presented the most significant association with HNC (OR = 10.22 and 10.38, respectively, p < 0.001). Cd level in blood sample of cases that are occupationally exposed/tobacco users (smokers and chewers) were higher than that of non-occupationally exposed/nontobacco users (p < 0.001). The logistic regression model illustrated that HNC (LC + NPC) was significantly associated with blood levels of As (OR = 2.41, p < 0.001) and Cd (OR = 4.95, p < 0.001).

Quinestrol has shown potential for use in the fertility control of the plateau pika population of the Qinghai–Tibet Plateau. However, the environmental safety and fate of this compound are still obscure. Our study investigated degradation of quinestrol in a local soil and aquatic system for the first time. The results indicate that the degradation of quinestrol follows first-order kinetics in both soil and water, with a dissipation half-life of approximately 16.0 days in local soil. Microbial activity heavily influenced the degradation of quinestrol, with 41.2 % removal in non-sterile soil comparing to 4.8 % removal in sterile soil after incubation of 10 days. The half-lives in neutral water (pH 7.4) were 0.75 h when exposed to UV light (λ = 365 nm) whereas they became 2.63 h when exposed to visible light (λ > 400 nm). Acidic conditions facilitated quinestrol degradation in water with shorter half-lives of 1.04 and 1.47 h in pH 4.0 and pH 5.0 solutions, respectively. Moreover, both the soil and water treatment systems efficiently eliminated the estrogenic activity of quinestrol. Results presented herein clarify the complete degradation of quinestrol in a relatively short time. The ecological and environmental safety of this compound needs further investigation.

Photochemical advanced oxidation processes have been considered for the treatment of water and wastewater containing the herbicide atrazine (ATZ), a possible human carcinogen and endocrine disruptor. In this study, we investigated the effects of the photon emission rate and initial concentration on ATZ photolysis at 254 nm, an issue not usually detailed in literature. Moreover, the role of reactive oxygen species (ROS) is discussed. Photon emission rates in the range 0.87 × 10¹⁸–3.6 × 10¹⁸ photons L⁻¹ s⁻¹ and [ATZ]₀ = 5 and 20 mg L⁻¹ were used. The results showed more than 65 % of ATZ removal after 30 min. ATZ photolysis followed apparent first-order kinetics with k values and percent removals decreasing with increasing herbicide initial concentration. A fivefold linear increase in specific degradation rate constants with photon emission rate was observed. Also, regardless the presence of persistent degradation products, toxicity was efficiently removed after 60-min exposure to UV radiation. Experiments confirmed a noticeable contribution of singlet oxygen and radical species to atrazine degradation during photolysis. These results may help understand the behavior of atrazine in different UV-driven photochemical degradation treatment processes.