Pharmaceuticals such as nonsteroidal anti-inflammatory drugs (NSAIDs) and lipid regulators are being repeatedly detected at low concentrations (pg · mL⁻¹–ng · mL⁻¹) in the environment. A large fraction of these compounds are ionizable. Ionized compounds show different physico-chemical properties and environmental behavior in comparison to their neutral analogs; as a consequence, the quantification methods currently available, based on the neutral molecules, might not be suitable to detect the corresponding ionized compounds. To overcome this problem, we developed a specific analytical method to quantify NSAIDs and lipid regulators (i.e., ibuprofen, diclofenac, naproxen, and clofibric acid) and their ionized compounds. This method is based on three steps: (1) the extraction of the organic compounds with an organic solvent assisted with an ultrasonic probe, (2) the cleaning of the extracts with a dispersive SPE with C₁₈, and (3) the determination of the chemical compounds by GC-MS (prior derivatization of the analytes). We demonstrated that the proposed method can successfully quantify the pharmaceuticals and their ionized compounds in aqueous samples, lumpfish eggs, and zebrafish eleutheroembryos. Additionally, it allows the extraction and the cleanup of extracts from small samples (0.010 g of wet weight in pools of 20 larvae) and complex matrixes (due to high lipid content) and can be used as a basis for bioaccumulation assays performed with zebrafish eleutheroembryos in alternative to OECD test 305.

During ovary maturation of crabs, vitellogenin (Vg), a precursor molecule of vitellin (Vn) needed for embryogenesis, can be produced in large quantities in the hepatopancreas and then transported to the ovary by the hemolymph. In the present study, effects of Cd on Vg accumulation in the hepatopancreas and Vg transportation of the freshwater crab Sinopotamon henanense were investigated. We also studied the impacts of Cd on the mRNA expression of genes involved in energy metabolism, protein metabolism, and metallothionein (MT) and glutathione (GSH) synthesis. After Cd treatment, the Vg concentration and the Vg mRNA expression in the hepatopancreas were downregulated. Pearson’s correlation coefficient showed that the Vg level in the hepatopancreas correlated positively with those of the ovary and hemolymph (correlation coefficients 0.844 and 0.749, respectively), suggesting that the Vg transport from the hepatopancreas to the ovary can be impaired by Cd. The levels of carbohydrate and protein in the hepatopancreas of Cd-exposed crabs were decreased, and an inhibited protein metabolism was also observed. Energy production related isocitrate dehydrogenase and cytochrome C oxidase mRNA expressions, and MT and GSH synthesis increased after 10 days of Cd treatment and decreased after 20 days. Cd also caused a time-dependent upregulation of malondialdehyde. Our findings showed that Cd decreased Vg accumulation in the hepatopancreas due to partially excessive energy consumption and an activated defense system in the hepatopancreas, suggesting a possible regulatory mechanism in S. henanense which is the competitive advantage of energy reserves in metabolic Cd stress responses over the high-energy flux during vitellogenesis to ensure a continuous supply of metabolic energy. Moreover, the damage of Vg accumulation in the hepatopancreas caused by Cd could lead to an insufficient accumulation of Vn in the ovary and cause a retardation of oocyte development.

We characterized humic substances (HS) extracted from a Cu-contaminated soil without compost addition (C) or amended with a wheat straw-based compost (WSC) (H1), co-composted with Fe₂O₃ (H2), or co-composted with an allophane-rich soil (H3). Extracted HS were characterized under electron microscopy (SEM/TEM), energy-dispersive X-ray (X-EDS), and Fourier transform infrared (FTIR) spectroscopy. In addition, HS extracted from WSC (H4) were characterized at pH 4.0 and 8.0 with descriptive purposes. At pH 4.0, globular structures of H4 were observed, some of them aggregating within a large network. Contrariwise, at pH 8.0, long tubular and disaggregated structures prevailed. TEM microscopy suggests organo-mineral interactions at scales of 1 to 200 nm with iron oxide nanoparticles. HS extracted from soil–compost incubations showed interactions at nanoscale with minerals and crystal compounds into the organic matrix of HS. Bands associated to acidic functional groups of HS may suggest potential sorption interactions with transition metals. We conclude that metal ions and pH have an important role controlling the morphology and configuration of HS from WSC. Characterization of H4 extracted from WSC showed that physicochemical protection of HS could be present in composting systems treated with inorganic materials. Finally, the humified fractions obtained from compost-amended soils may have an important effect on metal-retention, supporting their potential use in metal-contaminated soils.

The occurrence and atmospheric behavior of tri- to deca-polybrominated diphenyl ethers (PBDEs) were investigated during a 2-week campaign concurrently conducted in July 2012 at four background sites around the Aegean Sea. The study focused on the gas/particle (G/P) partitioning at three sites (Ag. Paraskevi/central Greece/suburban, Finokalia/southern Greece/remote coastal, and Urla/Turkey/rural coastal) and on the size distribution at two sites (Neochorouda/northern Greece/rural inland and Finokalia/southern Greece/remote coastal). The lowest mean total (G + P) concentrations of ∑₇PBDE (BDE-28, BDE-47, BDE-66, BDE-99, BDE-100, BDE-153, BDE-154) and BDE-209 (0.81 and 0.95 pg m⁻³, respectively) were found at the remote site Finokalia. Partitioning coefficients, K P, were calculated, and their linear relationships with ambient temperature and the physicochemical properties of the analyzed PBDE congeners, i.e., the subcooled liquid pressure (P L°) and the octanol-air partition coefficient (K OA), were investigated. The equilibrium adsorption (P L°-based) and absorption (K OA-based) models, as well as a steady-state absorption model including an equilibrium and a non-equilibrium term, both being functions of log K OA, were used to predict the fraction Φ of PBDEs associated with the particle phase. The steady-state model proved to be superior to predict G/P partitioning of BDE-209. The distribution of particle-bound PBDEs across size fractions < 0.95, 0.95–1.5, 1.5–3.0, 3.0–7.2, and > 7.2 μm indicated a positive correlation between the mass median aerodynamic diameter and log P L° for the less brominated congeners, whereas a negative correlation was observed for the high brominated congeners. The potential source regions of PBDEs were acknowledged as a combination of long-range transport with short-distance sources.

The photocatalytic reduction of Cr(VI) using pyrolytic char/TiO₂ (PC/TiO₂) composite catalyst under simulated solar irradiation was studied. Response surface methodology (RSM) and experimental design were used for modeling the removal kinetics and for the optimization of operational parameters. RSM was developed by considering a central composite design with four input variable, i.e. catalyst concentration, initial concentration of Cr(VI), pH, and % (v/v) methanol concentration for assessing individual and interactive effects. A quadratic model was established as a functional relationship between four independent variables and the removal efficiency of Cr(VI). It was found that all selected variables have significant effect on Cr(VI) removal efficiency; however, the pH, the % concentration of methanol, and their interaction exhibited the major effects. Within the studied experimental ranges, the optimum conditions for maximum Cr(VI) removal efficiency (72.1 %) after 60 min of photocatalytic treatment were: catalyst concentration 55 mg L⁻¹, Cr(VI) concentration 20 mg L⁻¹, pH 4, and 5 % (v/v) methanol concentration. Under optimum conditions, Cr(VI) reductive removal followed pseudo-first-order kinetics, and nearly complete removal took place within 90 min. The results revealed the feasibility and the effectiveness of PC/TiO₂ as photocatalyst in reduction reactions due to their ability of e⁻–h⁺ pair separation increasing the transfer of the photogenerated e⁻ to the catalyst’s surface and thus the reduction of Cr(VI).

Co-phytoremediation of both trace elements and polycyclic aromatic hydrocarbons (PAH) is an emerging technique to treat multi-contaminated soils. In this study, root morphological and structural features of the heavy metal hyperaccumulator Noccaea caerulescens, exposed to a model PAH phenanthrene (PHE) in combination with cadmium (Cd), were observed. In vitro cultivated seedlings were exposed to 2 mM of PHE and/or 5 μM of Cd for 1 week. Co-phytoremediation effectiveness appeared restricted because of a serious inhibition (about 40%) of root and shoot biomass production in presence of PHE, while Cd had no significant adverse effect on these parameters. The most striking effects of PHE on roots were a decreased average root diameter, the inhibition of cell and root hair elongation and the promotion of lateral root formation. Moreover, endodermal cells with suberin lamellae appeared closer to the root apex when exposed to PHE compared to control and Cd treatments, possibly due to modified lateral root formation. The stage with well-developed suberin lamellae was not influenced by PHE whereas peri-endodermal layer development was impaired in PHE-treated plants. Many of these symptoms were similar to a water-deficit response. These morphological and structural root modifications in response to PHE exposition might in turn limit Cd phytoextraction by N. caerulescens in co-contaminated soils.

Discharge of organic waste results in high nutrient pollution of the water bodies which is a major menace to the environment. A high quantity of nutrients such as ammonia causes a reduction in the dissolved oxygen level and induces algal growth in the water bodies. Water quality models have been the tools to evaluate the rate at which streams can disperse the pollutants they receive. Many water quality models are flawed either because of their inadequacy to completely simulate the advection component of the pollutant transport, or because of the limited application of the models, due to inaccurate estimation of model parameters. The hybrid cell in series (HCIS) developed by Ghosh et al. (2004) has been able to overcome such difficulties associated with the mixing cell-based models. Thus, the current study focuses on developing an analytical solution for the pollutant transport of the ammonia concentration through the plug flow, the first and second well-mixed cells of the HCIS model. The HCIS model coupled with the first order kinetic equation for ammonia nutrient was developed to simulate the ammonia pollutant concentration in the water column. The ammonia concentration at various points along the river system was assessed by considering the effects of the transformation of ammonia to nitrite, the uptake of ammonia by the algae, the respiration rate of the algae and the input of benthic source to the ammonia concentration in the water column. The proposed model was tested using synthetic data, and the HCIS-NH₃ model simulations for spatial and temporal variation of ammonia pollutant transport were analysed. The simulated results of the HCIS-NH₃ model agreed with the Fickian-based advection-dispersion equation (ADE) for simulating ammonia concentration solved using an explicit finite difference scheme. The HCIS-NH₃ model also showed a good agreement with the observed data from the Umgeni River, except during rainy periods.

Beijing-Tianjin-Hebei (BTH) region in China is affected seriously by the hazy weather that has a large impact on human health. PM₂.₅ is one of the most important reasons for hazy weather. Understanding the PM₂.₅ emission characteristics from different types of heavy-duty trucks (HDTs) is valuable in policies and regulations to improve urban air quality and mitigate vehicle emission in China. The investigation and analysis on HDT population and PM₂.₅ emission in BTH region are carried out. The results show that the population and PM₂.₅ emission of HDTs in BTH has risen for the last four consecutive years, from 404 thousand and 1795 tons in 2012 to 551 thousand and 2303 tons in 2015. The PM₂.₅ emission from HDTs in Hebei is about 10 times more than that of Beijing and 9 times more than that of Tianjin. The proportion of natural gas HDTs is about 5%; however, its PM₂.₅ emission only accounts for 0.94% in 2015, which indicates the utilization of HDTs powered by natural gas facilitate PM₂.₅ mitigation more than diesel in BTH. The tractor and pickup trucks are the main source of PM₂.₅ emission from different types of HDT, while special and dump trucks are relatively clean. This study has provided insights for management method and policy-making of vehicle in terms of environmental demand.

Purified terephthalic acid (PTA) plant of a petrochemical unit generates wastewater having high pollution load. Acid treatment of this wastewater reduces the chemical oxygen demand (COD) load by more than 50%, still leaving substantial COD load (>1500 mg/L) which should be removed. The present study reports on the use of a bio-waste-adsorbent bagasse fly ash (BFA) for the reduction of COD and other recalcitrant acids from this wastewater. The BFA showed basic character and was mesoporous with a BET specific surface area of 82.4 m²/g. Optimum conditions for the adsorptive treatment of acid-pretreated PTA wastewater were found to be as follows: initial pH (pHᵢ) = 4, BFA dosage = 15 g/L, and contact time = 3 h. Adsorption treatment resulted in 58.2% removal of COD, 96.3% removal of terephthalic acid (TA), and 99.9% removal of benzoic acid (BA). TA and BA were removed from the pretreated PTA wastewater through precipitation and sedimentation of un-dissociated acid molecules inside the mesopores of the BFA. The results showed that the COD removed by the BFA followed pseudo-second-order kinetics. Equilibrium sorption data were best correlated by the Freundlich isotherm. The process of adsorptive removal of COD was found to be exothermic. The change in the Gibbs free energy was found to be negative, suggesting that the adsorption process is spontaneous and feasible for the treatment of PTA wastewater.

Aminopolyphosphonates (AAPs) are commonly used industrial complexones of metal ions, which upon the action of biotic and abiotic factors undergo a breakdown and release their substructures. Despite the low toxicity of AAPs towards vertebrates, products of their transformations, especially those that contain phosphorus and nitrogen, can affect algal communities. To verify whether such chemical entities are present in water ecosystems, much effort has been made in developing fast, inexpensive, and reliable methods for analyzing phosphonates. However, unfortunately, the methods described thus far require time-consuming sample pretreatment and offer relatively high values of the limit of detection (LOD). The aim of this study was to develop an analytical approach to study the environmental fate of AAPs. Four phosphonic acids, N,N-bis(phosphonomethyl)glycine (GBMP), aminotris(methylenephosphonic) acid (ATMP), hexamethylenediamine-N,N,N′,N′-tetrakis(methylphosphonic) acid (HDTMP), and diethylenetriamine penta(methylenephosphonic) acid (DTPMP) were selected and examined in a water matrix. In addition, the susceptibility of these compounds to biotransformations was tested in colonies of five freshwater cyanobacteria—microorganisms responsible for the so-called blooms in the water. Our efforts to track the AAP decomposition were based on derivatization of N-alkyl moieties with p-toluenesulfonyl chloride (tosylation) followed by chromatographic (HPLC-UV) separation of derivatives. This approach allowed us to determine seven products of the breakdown of popular phosphonate chelators, in nanomolar concentrations and in one step. It should be noted that the LOD of four of those products, aminemethylphosphonic acid (AMPA), N-phosphomethyl glycine (NPMG), N-(methyl)aminemethanephosphonic acid (MAMPA), and N-(methyl) glycine (SAR), was set below the concentration of 50 nM. Among those substances, N-(methylamino)methanephosphonic acid (MAMPA) was identified for the first time as the product of decomposition of the examined aminopolyphosphonates.