For the synthesis of a highly active TiO₂-chitosan nanocomposite, pH plays a crucial role towards controlling its morphology, size, crystallinity, thermal stability, and surface adsorption properties. The presence of chitosan (CS) biopolymer facilitates greater sustainability to the photoexcited electrons and holes on the catalysts’ surface. The variation of synthesis pH from 2 to 5 resulted in different physico-chemical and photocatalytic properties, whereby a pH of 3 resulted in TiO₂-chitosan nanocomposite with the highest photocatalytic degradation (above 99 %) of methylene orange (MO) dye. This was attributed to the efficient surface absorption properties, high crystallinity, and the presence of reactive surfaces of –NH₂ and –OH groups, which enhances the adsorption-photodegradation effect. The larger surface oxygen vacancies coupled with reduced electron-hole recombination further enhanced the photocatalytic activity. It is undeniable that the pH during synthesis is critical towards the development of the properties of the TiO₂-chitosan nanocomposite for the enhancement of photocatalytic activity.

Sediments from the Castilseras reservoir, located downstream on the Valdeazogues River in the Almadén mercury district, were collected to assess the potential contamination status related to metals(oids) associated with river sediment inputs from several decommissioned mines. Metals(oids) concentrations in the reservoir sediments were investigated using different physical and chemical techniques. The results were analyzed by principal component analysis (PCA) to explain the correlations between the sets of variables. The degree of contamination was evaluated using the enrichment factor (EF) and the geoaccumulation index (Igeo). PCA revealed that the silty fraction is the main metals(oids) carrier in the sediments. Among the potentially harmful elements, there is a group (Al, Cr, Cu, Fe, Mn, Ni, and Zn) that cannot be strictly correlated to the mining activity since their concentrations depend on the lithological and edaphological characteristics of the materials. In contrast, As, Co, Hg, Pb, and S showed significant enrichment and contamination, thus suggesting relevant contributions from the decommissioned mines through fluvial sediment inputs. As far as Hg and S are concerned, the high enrichment levels pose a question concerning the potential environmental risk of transfer of the organic forms of Hg (mainly methylmercury) from the bottom sediments to the aquatic food chain.

The environmental fate of polybrominated diphenyl ethers (PBDEs), a group of flame retardants that are considered to be persistent organic pollutants (POPs), around the Zhuoshui River and Changhua County regions of Taiwan was assessed. An investigation into emissions, partitioning, and fate of selected PBDEs was conducted based on the equilibrium constant (EQC) fugacity model developed at Trent University, Canada. Emissions for congeners PBDE 47, PBDE 99, and PBDE 209 to air (4.9–92 × 10⁻³ kg/h), soil (0.91–17.4 × 10⁻³ kg/h), and water (0.21–4.04 × 10⁻³ kg/h), were estimated by modifying previous models on PBDE emission rates by considering both industrial and domestic rates. It was found that fugacity modeling can give a reasonable estimation of the behavior, partitioning, and concentrations of PBDE congeners in and around Taiwan. Results indicate that PBDE congeners have a high affinity for partitioning into sediments then soils. As congener number decreases, the PBDEs then partition more readily into air. As the degree of bromination increases, congeners more readily partition to sediments. Sediments may then act as a long-term source of PBDEs which can be released back into the water column due to resuspension during storm events.

The occurrence of 32 pharmaceuticals and 14 UV filters in swimming pools and spas was studied. Fifty-one water samples were collected from 17 pools located in sport centres and hotels in Catalonia, Spain. The samples were analysed by liquid chromatography-tandem mass spectrometry. The pharmaceuticals atenolol, carbamazepine, hydrochlorothiazide, metronidazole, ofloxacin, sulfamethoxazole, acetaminophen, ibuprofen, ketoprofen and phenazone were measured in water samples at concentrations higher than their limit of quantification (LOQ). The highest concentration of any individual pharmaceutical was measured for the diuretic hydrochlorothiazide (904 ng/L). The most frequently detected pharmaceutical was carbamazepine, as it was observed in more than half of all the water samples measured (53 %, 27/51). The UV filters at concentrations higher than LOQ in water samples were BP1, BP2, BP3, BP8, THB, 4DHB, 4MBC, OD-PABA, 1HBT, MeBT and DMeBT. The highest concentration of UV filter observed was 4MBC (69.3 ng/L) while the most frequent UV filters in the samples were 1HBT (59 %, 30/51). The results also showed that pharmaceuticals and UV filters were most frequently found in spas. Finally, from a water treatment technology perspective, the lowest occurrence of pharmaceuticals was in the pools applying sand filters followed by disinfection by sodium hypochlorite, while the lowest occurrence of UV filters was in the pools applying coagulation, sand filtration, UV and salt electrolysis.

The lipid regulator gemfibrozil (GEM) has been reported to be persistent in conventional wastewater treatment plants. This study investigated the photolytic behavior, toxicity of intermediate products, and degradation pathways of GEM in aqueous solutions under UV irradiation. The results demonstrated that the photodegradation of GEM followed pseudo-first-order kinetics, and the pseudo-first-order rate constant was decreased markedly with increasing initial concentrations of GEM and initial pH. The photodegradation of GEM included direct photolysis via ³GEM* and self-sensitization via ROS, where the contribution rates of degradation were 0.52, 90.05, and 8.38 % for ·OH, ¹O₂, and ³GEM*, respectively. Singlet oxygen (¹O₂) was evidenced by the molecular probe compound, furfuryl alcohol (FFA), and was identified as the primary reactive species in the photolytic process. The steady-state concentrations of ¹O₂ increased from (0.324 ± 0.014) × 10⁻¹² to (1.021 ± 0.040) × 10⁻¹² mol L⁻¹, as the initial concentrations of GEM were increased from 5 to 20 mg L⁻¹. The second-order rate constant for the reaction of GEM with ¹O₂ was calculated to be 2.55 × 10⁶ M⁻¹ s⁻¹. The primary transformation products were identified using HPLC-MS/MS, and possible photodegradation pathways were proposed by hydroxylation, aldehydes reactions, as well as the cleavage of ether side chains. The toxicity of phototransformation product evaluation revealed that photolysis potentially provides a critical pathway for GEM toxicity reduction in potable water and wastewater treatment facilities.

The present study was designed to study the effect of brick kilns emissions on the reproductive health and biochemical status of brick kiln workers and people living in the area near brick kilns. Body mass index (BMI) was significantly reduced in brick makers, carriers, and bakers compared to the control. Red blood cells count and hematocrit (%) were significantly high in brick bakers while MCH was significantly reduced in brick makers and brick bakers. Heavy metals (lead, cadmium, and chromium) concentration in whole blood of the brick kiln workers were significantly higher as compared to the control. Antioxidant enzymes (CAT, SOD, POD, GSH, and GR) were significantly reduced in brick kiln workers as compared to the control while TBARS level were significantly high in brick bakers as compared to the control. Plasma leutinizing hormone (LH) was significantly high in brick bakers while testosterone concentrations were significantly reduced in brick makers, carriers, and bakers. The present study shows that brick kiln workers and people living in the brick kiln vicinity are exposed to heavy metals and other pollutants that is a serious threat to their health. Alternate technology is needed to be developed and brick kilns should be replaced.

In this paper, the data for ten water quality variables collected during 2009 at 75 monitoring sites along the river network of Serbia are considered. The results are alarming because 48 % of the studied sites were contaminated by Ni, Mn, Pb, As, and nutrients, which are key factors impairing the water quality of the rivers in Serbia. Special attention should be paid to Zn and Cu, listed in the priority toxic pollutants of US EPA for aquatic life protection. The employed Q-model cluster analysis grouped the data into three major pollution zones (low, moderate, and high). Most sites classified as “low pollution zones” (LP) were in the main rivers, whereas those classified as “moderate and high pollution zones” (MP and HP, respectively) were in the large and small tributaries/hydro-system. Principal component analysis/factor analysis (PCA/FA) showed that the dissolved metals and nutrients in the Serbian rivers varied depending on the river, the heterogeneity of the anthropogenic activities in the basins (influenced primarily by industrial wastewater, agricultural activities, and urban runoff pollution), and natural environmental variability, such as geological characteristics. In LP dominated non-point source pollution, such as agricultural and urban runoff, whereas mixed source pollution dominated in the MP and HP zones. These results provide information to be used for developing better pollution control strategies for the river network of Serbia.

The rate of degradation of enrofloxacin in broiler chicken manure has been characterized in the laboratory according to the CVMP guideline on determining the fate of veterinary medicinal products in manure. Degradation was followed in a flow-through system under aerobic and anaerobic conditions, in the dark and in the presence of light. The rate of degradation of enrofloxacin and the formation of its degradation products are dependent on laboratory conditions. A rapid degradation of enrofloxacin in the dark was noticed, where a shorter degradation half-life under aerobic (DT₅₀ = 59.1 days), comparing to anaerobic conditions (DT₅₀ = 88.9 days), was determined. The presence of light slowed down the enrofloxacin degradation half-life, which was significantly shorter under aerobic (DT₅₀ = 115.0 days), comparing to anaerobic conditions (DT₅₀ = 190.8 days). Desethylene-enrofoxacin was the only degradation product formed, its concentrations ranged from 2.5 to 14.9 %. The concentration of the degradation product was approximately 2.5-fold higher under aerobic conditions. Enrofloxacin degradation in sterile manure incubated under sterile conditions was marginal comparing to non-sterile conditions; after 120 days of incubation, approximately 80 % of enrofloxacin was still present in manure and only 1 % of desethylene-enrofloxacin was formed. The present work demonstrates that enrofloxacin degradation in chicken manure is relatively fast when incubated in the dark under aerobic conditions which is the recommended incubation system for chicken manure according to CVMP guideline.

The presence of potentially toxic elements (PTEs) may hinder a more widespread application of biosolids in agriculture. At present, the European Directive 86/278/CEE limit the total concentrations of seven metals (Cu, Cr, Ni, Pb, Zn, Cd and Hg) in agricultural soils and in sewage sludges used as fertilizers but it has not taken into consideration the potential impacts of other emerging micropollutants that may be present in the biosolids as well as their mobility. The aim of this study was to evaluate the accumulation and mobility of 13 elements (including regulated metals and other inorganic species) in agricultural soils repeatedly amended with biosolids for 15 years. Firstly, three digestions programs using different acid mixtures were tested to evaluate the most accurate and efficient method for analysis of soil and sludge. Results demonstrated that sewage sludge application increased concentrations of Pb and Hg in soil, but values did not exceed the quality standard established by legislation. In addition, other elements (As, Co, Sb, Ag, Se and Mn) that at present are not regulated by the Spanish and European directives were identified in the sewage sludge, and significant differences were found between Ag content in soils amended with biosolids in comparison with control soils. This fact can be related to the increasing use of silver nanoparticles in consumer products due to their antibacterial properties. Results from the leaching tests show up that, in general, the mobility degree for both regulated and non-regulated elements in soils amended with biosolids was quite low (<10 %).