Prior investigations identified an association between low-level blood arsenic (As) and bladder cancer risk among Tunisian men but questions remain regarding confounding by cadmium (Cd), a well-established bladder carcinogen. A case-control study of Tunisian men was re-examined to assess the levels of cadmium in blood and reparse the association between the simultaneous exposure to these metals and bladder cancer risk. Levels of blood Cd were significantly twice higher among cases than in controls (P < 0.05) and were positively correlated with smoking and age. Additionally, analysis of metal levels among non-smokers according to the region of residence showed very high blood Cd and As levels for the coastal regions of Sfax and central Tunisia. After controlling for potential confounders, for low blood As levels (<0.67 μg/L), the OR for blood Cd was 4.10 (95 % CI 1.64-10.81), while for higher levels (>0.67 μg/L), it was reduced to 2.10 (CI, 1.06-4.17). Adjustment for Cd exposure did not alter the risk associated to As exposure. This study is the first to report the relationship between Cd exposure and risk of bladder cancer occurrence in interaction with smoking and As exposure. Smoking is shown to be the main exposure source to Cd in the Tunisian population but also environmental pollution seems to be responsible of Cd exposure among non-smokers. Exposure assessment studies encompassing a wider population are needed.

Concentrations of Hg, Pb, Cd, and Cr in 240 shellfish including oyster, short-necked clam, razor clam, and mud clam collected from six administrative regions in Xiamen of China were measured. The daily intakes of heavy metals through the consumption of shellfish were estimated based on both of the metal concentrations in shellfish and the consuming amounts of shellfish. In addition, the target hazard quotients (THQ) were used to evaluate the potential risk of heavy metals in shellfish on human body. Results showed that the concentrations of heavy metals in shellfish ranged at the following sequence: Cr > Cd > Pb > Hg. The concentrations of Hg and Pb in most samples were below the limits (0.3 mg kg⁻¹ for Hg and 0.5 mg kg⁻¹ for Pb) of national standard (GB 18406.4-2001) set in China. About 57 % of samples were found to contain more than 0.1 mg kg⁻¹ of Cd, in which the highest level was found in oyster from Xiangan with a value of 1.21 mg kg⁻¹. The average concentrations of Cd in oyster and mud clam samples were 0.338 and 0.369 mg kg⁻¹, respectively, which were significantly higher (p < 0.05) than those in the samples of short-necked clam and razor clam. The highest concentration of Cr was found to present in short-necked clam from Jimei with a value of 10.4 mg kg⁻¹, but a mean value of 1.95 mg kg⁻¹ in all the shellfish was observed, and no significant difference was found among the different sampling regions. The calculated daily intakes of Hg, Pb, Cd, and Cr through consuming the shellfish were 0.005, 0.122, 0.137, and 1.20 μg kg⁻¹ day⁻¹, respectively, which accounted for 2.19, 3.42, 13.7, and 40.1 % of the corresponding tolerable limits suggested by the Joint FAO/WHO Expert Committee on Food Additives. The THQ values of the four metals were far below 1 for most samples, except for those of Cd and Cr in the four shellfish species with the mean values of 0.132 and 0.385, respectively. The highest THQ values of Cd were observed in the species of oyster (0.719) and mud clam (0.568). But the high THQ values of Cr observed in all the four species were derived from the applied reference dose (RfD) data of Cr(VI) due to the unavailable RfD value of total Cr. The results indicate that the intakes of heavy metals by consuming shellfish collected from Xiamen of China do not present an appreciable hazard risk on human health, but attention should be paid to consuming those with relatively high THQ values, such as oyster, mud clam, and short-necked clam.

Mussels are widespread in coastal environments and experience various physical, chemical, and bacteriological conditions. Owing to the increase of coastal urbanization, mussels are now commonly exposed not only to indigenous bacteria, but also to enteric bacteria originating from pulsed and chronic sewage discharges into coastal environments. Due to its broad resilience to environmental variations, the blue mussel Mytilus edulis is commonly used as an indicator of environmental quality in bio-monitoring programs. However, since mussel immune system capabilities may be affected by the presence of exogenous fecal bacteria in coastal seawater subjected to sewage discharges, we aimed to determine the effect of in vivo bacterial challenges on mussels' immune competency by using two exogenous enteric bacterial strains, Escherichia coli and Enterococcus faecalis, and an indigenous bacterial strain Vibrio splendidus (as control). Bacterial strains were tested individually, by injection into the posterior adductor muscle at three different cell densities (10², 10³, and 10⁴ cells). Unlike classic in vitro experiments using higher bacterial concentrations, neither the enteric bacteria nor the indigenous strain induced significant increase or decrease of either cell-mediated (phagocytosis, reactive oxygen species, and NO ₓ production) or humoral components (prophenoloxidase-like, acid phosphatase, and L-leucine-aminopeptidase production) of the immune system. This study demonstrates that, at low concentrations, E. coli and E. faecalis do not represent an additional threat that could impair M. edulis immune competency and, as a consequence, its potential of survival in coastal areas subjected to sewage discharges.

Arsenic contamination of groundwater is a major threat to human beings globally. Among various methods available for arsenic removal, adsorption is fast, inexpensive, selective, accurate, reproducible and eco-friendly in nature. The present paper describes removal of arsenate from water on zirconium oxide-coated sand (novel adsorbent). In the present work, zirconium oxide-coated sand was prepared and characterised by infrared and X-ray diffraction techniques. Batch experiments were performed to optimise different adsorption parameters such as initial arsenate concentration (100-1,000 μg/L), dose (1-8 g/L), pH of the solution (2-14), contact time (15-150 min.), and temperature (20, 30, 35 and 40 °C). The experimental data were analysed by Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherm models. Furthermore, thermodynamic and kinetic parameters were evaluated to know the mode of adsorption between ZrOCMS and As(V). The maximum removal of arsenic, 97 %, was achieved at initial arsenic concentration of 200 μg/L, after 75 min at dosage of 5.0 g/L, pH 7.0 and 27 ± 2 °C. For 600 μg/L concentration, the maximum Langmuir monolayer adsorption capacity was found to be 270 μg/g at 35 °C. Kinetic modelling data indicated that adsorption process followed pseudo-second-order kinetics. The mechanism is controlled by liquid film diffusion model. Thermodynamic parameter, ΔH°, was -57.782, while the values of ΔG° were -9.460, -12.183, -13.343 and -13.905 kJ/mol at 20, 30, 35 and 40 °C, respectively, suggesting exothermic and spontaneous nature of the process. The change in entropy, ΔS° = -0.23 kJ/mol indicated that the entropy decreased due to adsorption of arsenate ion onto the solid adsorbent. The results indicated that the reported zirconium oxide-coated marine sand (ZrOCMS) was good adsorbent with 97 % removal capacity at 200 μg/L concentration. It is interesting to note that the permissible limit of arsenic as per World Health Organization is 10 μg/L, and in real situation, this low concentration can be achieved through this adsorbent. Besides, the adsorption capacity showed that this adsorbent may be used for the removal of arsenic from any natural water resource.

Ammonium ions are one of the most encountered nitrogen species in polluted water bodies. High level of ammonium ion in aqueous solution imparts unpleasant taste and odor problems, which can interfere with the life of aquatics and human population when discharged. Many chemical methods are developed and being used for removal of ammonium ion from aqueous solution. Among various techniques, adsorption was found to be the most feasible and environmentally friendly with the use of natural-activated adsorbents. Hence, in this study, coconut shell-activated carbon (CSAC) was prepared and used for the removal of ammonium ion by adsorption techniques. Ammonium chloride (analytical grade) was purchased from Merck Chemicals for adsorption studies. The CSAC was used to adsorb ammonium ions under stirring at 100 rpm, using orbital shaker in batch experiments. The concentration of ammonium ion was estimated by ammonia distillate, using a Buchi distillation unit. The influence of process parameters such as pH, temperature, and contact time was studied for adsorption of ammonium ion, and kinetic, isotherm models were validated to understand the mechanism of adsorption of ammonium ion by CSAC. Thermodynamic properties such as ∆G, ∆H, and ∆S were determined for the ammonium adsorption, using van't Hoff equation. Further, the adsorption of ammonium ion was confirmed through instrumental analyses such as SEM, XRD, and FTIR. The optimum conditions for the effective adsorption of ammonium ion onto CSAC were found to be pH 9.0, temperature 283 K, and contact time 120 min. The experimental data was best followed by pseudosecond order equation, and the adsorption isotherm model obeyed the Freundlich isotherm. This explains the ammonium ion adsorption onto CSAC which was a multilayer adsorption with intraparticle diffusion. Negative enthalpy confirmed that this adsorption process was exothermic. The instrumental analyses confirmed the adsorption of ammonium ion onto CSAC.

In the present study, the photocatalytic degradation of Reactive Red 195 (RR195) from aqueous samples under UV-A irradiation by using anatase/brookite TiO₂ (A/B TiO₂) mesoporous nanoparticles has been investigated. Batch experiments were conducted to study the effects of the main parameters affecting the photocatalytic process. The effects and interactions of most influenced parameters, such as substrate concentration and catalyst load, were evaluated and optimized by using a central composite design model and a response surface methodology. The results indicated that the dye degradation efficiency in the experimental domain investigated was mainly affected by the tested variables, as well as their interaction effects. Analysis of variance showed a high coefficient of determination value (R ² = 0.9947), thus ensuring a satisfactory adjustment of the first-order regression model (2FI model) with the experimental data. The obtained results also indicate that catalyst loading plays an important role in determining the removal efficiency of RR195 attributable to both photodegradation and adsorption process. Under optimal conditions (initial dye concentration (50 mg/L) and catalyst loading (2,000 mg/L), A/B TiO₂ showed similar removal efficiency compared to that of commercial titania (Degussa P25). Also, at these conditions, complete degradation of RR195 can be achieved by both catalysts within 15 min under UV-A irradiation. The experiments demonstrated that dye removal on the prepared A/B TiO₂ was facilitated by the synergistic effects between adsorption and photocatalysis. Photocatalytic mineralization of RR195 was monitored by total organic carbon. The recycling experiments confirmed the stability of the catalyst.

Degradation of three sulfonamides (SAs), namely sulfamethoxazole (SMX), sulfamethazine (SMZ), and sulfadimethoxine (SDM) in surface water and sediments collected from Taihu Lake and Dianchi Lake, China was investigated in this study. The surface water (5–10 cm) was collected from the east region of Taihu Lake, China. Two sets of degradation experiments were conducted in 3-L glass bottles containing 2 L of fresh lake water and 100 μg/L of individual SAs aerated by bubbling air at a rate of approximately 1.2 L/min, one of which was sterilized by the addition of NaN₃ (0.1 %). Sediment samples were taken from Taihu Lake and Dianchi Lake, China. For the sediment experiment, 5 g of sediment were weighed into a 50-mL glass tube, with 10 mg/kg of individual SAs. Different experimental conditions including the sediment types, sterilization, light exposure, and redox condition were also considered in the experiments. The three SAs degraded in lake water with half-lives (t ₁/₂) of 10.5–12.9 days, and the half-lives increased significantly to 31.9–49.8 days in the sterilized water. SMZ and SDM were degraded by abiotic processes in Taihu and Dianchi sediments, and the different experimental conditions and sediments characteristics had no significant effect on their declines. SMX, however, was mainly transformed by facultative anaerobes in Taihu and Dianchi sediments under anaerobic conditions, and the degradation rate of SMX in non-sterile sediment (t ₁/₂ of 9.6–16.7 days) were higher than in sterilized sediment (t ₁/₂ of 18.7–135.9 days). Under abiotic conditions, degradation of SMX in Dianchi sediment was faster than in Taihu sediment, probably due to the higher organic matter content and inorganic photosensitizers concentrations in Dianchi sediment. High initial SAs concentration inhibited the SAs degradation, which was likely related to the inhibition of microorganism activities by high SAs levels in sediments. Results from this study could provide information on the persistence of commonly used sulfanomides antibiotics in lake environment.

Beef and dairy products may be important vectors of human exposure to perfluoroalkyl acids (PFAAs), but the understanding of how PFAAs are accumulated and transferred through agricultural food chains is very limited. Here, the bioaccumulation of PFAAs in dairy cows receiving naturally contaminated feed and drinking water was investigated by conducting a mass balance of PFAAs for a herd of dairy cows in a barn on a typical Swedish dairy farm. It was assumed that the cows were able to reach steady state with their dietary intake of PFAAs. Perfluorooctane sulfonic acid (PFOS) and perfluoroalkyl carboxylic acids (PFCAs) with 8 to 12 carbons were detected in cow tissue samples (liver, muscle, and blood) at concentrations up to 130 ng kg(-1). Mass balance calculations demonstrated an agreement between total intake and excretion within a factor of 1.5 and consumption of silage was identified as the dominant intake pathway for all PFAAs. Biomagnification factors (BMFs) were highly tissue and homologue specific. While BMFs of PFOS and PFCAs with 9 and 10 fluorinated carbons in liver ranged from 10 to 20, perfluorooctanoic acid (PFOA) was not biomagnified (BMF < 1) in any of the investigated tissues. Biotransfer factors (BTFs; defined as the concentration in tissue divided by the total daily intake) were calculated for muscle and milk. Log BTFs ranged from -1.95 to -1.15 day kg(-1) with the highest BTF observed for PFOS in muscle. Overall, the results of this study suggest that long-chain PFAAs have a relatively high potential for transfer to milk and beef from the diet of dairy cows. However, a low input of PFAAs to terrestrial systems via atmospheric deposition and low bioavailability of PFAAs in soil limits the amount of PFAAs that enter terrestrial agricultural food chains in background contaminated environments and makes this pathway less important than aquatic exposure pathways. The BTFs estimated here provide a useful tool for predicting human exposure to PFAAs via milk and beef under different contamination scenarios.

The main disadvantage of using iron mineral in Fenton-like reactions is that the decomposition rate of organic contaminants is slower than in classic Fenton reaction using ferrous ions at acidic pH. In order to overcome these drawbacks of the Fenton process, chelating agents have been used in the investigation of Fenton heterogeneous reaction with some Fe-bearing minerals. In this work, the effect of new iron complexing agent, ethylenediamine-N,N'-disuccinic acid (EDDS), on heterogeneous Fenton and photo-Fenton system using goethite as an iron source was tested at circumneutral pH. Batch experiments including adsorption of EDDS and bisphenol A (BPA) on goethite, H₂O₂ decomposition, dissolved iron measurement, and BPA degradation were conducted. The effects of pH, H₂O₂ concentration, EDDS concentration, and goethite dose were studied, and the production of hydroxyl radical (•OH) was detected. The addition of EDDS inhibited the heterogeneous Fenton degradation of BPA but also the formation of •OH. The presence of EDDS decreases the reactivity of goethite toward H₂O₂ because EDDS adsorbs strongly onto the goethite surface and alters catalytic sites. However, the addition of EDDS can improve the heterogeneous photo-Fenton degradation of BPA through the propagation into homogeneous reaction and formation of photochemically efficient Fe-EDDS complex. The overall effect of EDDS is dependent on the H₂O₂ and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O ₂ •⁻ to generate Fe(II) species from Fe(III) reduction. Low concentrations of H₂O₂ (0.1 mM) and EDDS (0.1 mM) were required as optimal conditions for complete BPA removal. These findings regarding the capability of EDDS/goethite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.

Trichloroethylene (TCE) is one of the most hazardous organic pollutants in groundwater. Biochar produced from agricultural waste materials could serve as a novel carbonaceous adsorbent for removing organic contaminants from aqueous media. Biochars derived from pyrolysis of soybean stover at 300 °C and 700 °C (S-300 and S-700, respectively), and peanut shells at 300 °C and 700 °C (P-300 and P-700, respectively) were utilized as carbonaceous adsorbents to study batch aqueous TCE remediation kinetics. Different rate-based and diffusion-based kinetic models were adopted to understand the TCE adsorption mechanism on biochars. With an equilibrium time of 8-10 h, up to 69 % TCE was removed from water. Biochars produced at 700 °C were more effective than those produced at 300 °C. The P-700 and S-700 had lower molar H/C and O/C versus P-300 and S-300 resulting in high aromaticity and low polarity accompanying with high surface area and high adsorption capacity. The pseudo-second order and intraparticle diffusion models were well fitted to the kinetic data, thereby, indicating that chemisorption and pore diffusion were the dominating mechanisms of TCE adsorption onto biochars.