The increasing production and applications of graphene oxide (GO, a novel carbon nanomaterial) have raised numerous environmental concerns regarding its ecological risks. Triphenyl phosphate (TPhP) disperses in water and poses an increasing hazard to the ecosystem and human health. It is critical to study the environmental responses and molecular mechanisms of GO and TPhP together to assess both chemicals; however, this information is lacking. The present work revealed that GO promoted the bioaccumulation of TPhP in zebrafish larvae by 5.0%–24.3%. The TPhP-induced growth inhibition of embryos (malformation, mortality, heartbeat, and spontaneous movement) at environmentally relevant concentrations was significantly amplified by GO, and these results were supported by the downregulated levels of genes and proteins associated with cytoskeletal construction and cartilage and eye development. TPhP induced negligible alterations in the genes or proteins involved in oxidative stress and apoptosis, but those related proteins were all upregulated by GO. GO and TPhP coexposure activated the mTOR signaling pathway and subsequently promoted apoptosis in zebrafish by potentiating the oxidative stress induced by TPhP, presenting synergistic toxicity. These findings highlight the potential risks and specific molecular mechanisms of combining emerging carbon nanomaterials with coexisting organic contaminants.

This work has been conducted as an integrated approach to study the behavior of soils to the metals from sludge amendment. Bureau Commun Reference (BCR) methodology was used as an appropriate tool to harvest precious information about heavy metals evolution versus depth before and after sludge treatments. This three-step extraction procedure (i.e., BCR) may clarify the leaching or retention of heavy metals from the amended soils, as well as their risk level. Our results indicated that sludge applications has shown an increasing flux of heavy metals towards amended soils, of which Pb was the most abundant. Heavy metals mobility in control and amended soils showed that main influencing factors are pH and total organic carbon, especially for copper mobility. Almost all of the metals decreased with soil depth, except for Ni. Speciation of heavy metals in sludges showed that about 45% of Pb, Cu and Ni were associated with residual fraction; Cd was mainly bound to reducible fraction. Speciation forms in the control soil indicated that short term application of sludge has remobilized a fraction of heavy metals into their most labile forms (i.e., exchangeable and reducible fraction). Multivariate statistical analysis suggested that Cd, Zn, Pb and Cu preferentially accumulated in organic-rich surface horizons and clay layers where adsorption played an important role as a determining mechanism. Nevertheless, adsorption did not appear to be directly controlled by high pH values (pH > 7). From Cluster Analysis (CA), one can easily recognize that Pb, Zn and Cu movement in soil profiles were significantly affected by pH, especially residual fraction, labile fraction and reducible fraction.

Data from National Health and Nutrition Examination Survey for 2003–2014 for US children aged 6–11 years (N = 2097), adolescents aged 12–19 ears (N = 2642), and adults aged ≥ 20 years (N = 9170) were analyzed to investigate the effects of dietary, demographic, disease, lifestyle, and other factors on concentrations of nine metabolites of polycyclic aromatic hydrocarbons (PAH) in urine. PAHs analyzed were: 1-hydroxynaphthalene, 2-hydroxynaphthalene, 2-hydroxyfluorene, 3-hydroxyfluorene, 9-hydroxyfluorene, 1-hydroxyphenanthrene, 2-hydroxyphenanthrene, 3-hydroxyphenanthrene, and 1-hydroxypyrene. Adults with diabetes were found to have higher adjusted levels of 1-hydroxynaphthalene (4139 vs. 3622 ng/L, p < 0.01) than nondiabetics. Adults with albuminuria had higher adjusted levels of 1-hydroxynaphthalene (4140 vs.3621 ng/L, p < 0.01) and 2-hydroxynaphthalene (6039 vs. 5468 ng/L, p < 0.01) than those without albuminuria. Children with albuminuria had lower adjusted levels of 9-hydroxyfluorene (162 vs. 187 ng/L, p = 0.04), 1-hydroxyphenanthrene (92 vs. 108 ng/L, p < 0.01), and 1-hydroxypyrene (118 vs. 138 ng/L, p < 0.01) than those without albuminuria. The ratios of smoker to nonsmoker adjusted levels for adults varied from a low of 1.4 for 2-hydroxyphenanthrene to a high of 5.6 for 3-hydroxyfluorene. Exposure to environmental tobacco smoke at home was associated with higher levels of most OH-PAHs among children, adolescents, and adults. Consumption of red meat not processed at high temperatures was associated with increased levels of 1-hydroxypyrene (β = 0.00040, p = 0.01), 1-, 2-, and 3-hydroxyphenanthrene, 3-, and 9-hydroxyfluorene. Consumption of red meat processed at high temperatures was associated with increased levels of 2-hydroxynaphthalene (β = 0.00046, p = 0.02) among adults. Consumption of fish processed at high temperatures was associated with decreased levels of 1-hydroxynaphtahlene (β = − 0.00088, p < 0.01), 2-, 3-, and 9-hydroxyfluorene, 1-, 2-, and 3-hydroxyphenanthrene. Among adults, alcohol consumption and caffeine may be associated with increased levels of certain OH-PAHs. Oxidative stress and inflammation associated with exposure to PAHs are associated with albuminuria and have the potential to lead to the development of diabetes.

While Cox17 functions importantly in copper metalation of cytochrome c oxidase and integral mitochondrial architecture in vertebrates, rare studies have been performed regarding the developmental and physiological characters of vertebrate cox17 mutants. In this study, normal-like developmental phenotype was observed in both cox17Δ6−/− and cox17Δ4−/− homozygous zebrafish mutants, while gene ontology term and pathway analysis of the differentially expressed genes in both mutants showed enrichment in oxidoreductase activity, ion transport, histone methylation, MICOS complex, Wnt signaling, etc. This implied the occurrence of damage to the integral function of Cox17 and change of transcriptomes in the two mutants. Further qRT-PCR and WISH assays revealed the down-regulated expression of Wnt signaling and reduced expression of swim bladder marker genes in the two mutants. Moreover, copper stimulation induced no obvious increase in reactive oxygen species (ROS) or in the expression of hemoglobin marker genes, but further reduced the expression of swim bladder marker genes in the mutants. The integral data in this study suggest that: (1) cox17 mutants cannot activate the response of oxidoreductase to copper stimulation; (2) copper depends on the integral function of Cox17 to induce developmental defects in hemoglobin rather than swim bladder and (3) Wnt signaling but not ROS might mediate copper-induced swim bladder developmental defects in fish.

The boreoatlantic gonate squid (Gonatus fabricii) represents important prey for top predators—such as marine mammals, seabirds and fish—and is also an efficient predator of crustaceans and fish. Gonatus fabricii is the most abundant cephalopod in the northern Atlantic and Arctic Ocean but the trace element accumulation of this ecologically important species is unknown. In this study, trace element concentrations (Ag, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, and Zn) were analysed from the mantle muscle and the digestive gland tissue of juveniles, adult females, and adult males that were captured south of Disko Island off West-Greenland. To assess the feeding habitat and trophic position of this species, stable isotopes of carbon (δ13C) and nitrogen (δ15N) were measured in their muscle tissue. Mercury concentrations were positively correlated with size (mantle length) and trophic position. The Hg/Se ratio was assessed because Se has been suggested to play a protective role against Hg toxicity and showed a molar surplus of Se relative to Hg. Cadmium concentrations in the digestive gland were negatively correlated with size and trophic position (δ15N), which suggested a dietary shift from Cd-rich crustaceans towards Cd-poor fish during ontogeny. This study provides trace element concentration data for G. fabricii from Greenlandic waters, which represents baseline data for a northern cephalopod species. Within West-Greenland waters, G. fabricii appears to be an important vector for the transfer of Cd in the Arctic pelagic food web.

Irinotecan (CPT-11) is a water-soluble anticancer drug widely used to treat several types of cancer.Even if the metabolites of CPT-11 are well-known and investigated, only limited information is available in the literature about the formation of photo-degradation products that can naturally originate from sunlight irradiation when the drug is released in aqueous systems.CTP-11 solutions at 10.0 mg L−1 were irradiated by simulated sunlight. The intensity of the drug decreased by 90% after 7.5 days of irradiation and no significant reduction of absorbance values was observed after 13 days.A sensitive UHPLC-MS/MS method was developed employing a hybrid triple quadrupole/linear ion trap mass spectrometer, that is able to work in data-dependent acquisition mode and to obtain information about the compounds formed during the photoirradiation. Moreover, a selected reaction monitoring method was built using the MS/MS fragmentation pattern of the compounds previously investigated. The method was validated considering LOD, LOQ, linearity, precision, selectivity, recovery and matrix effect. LOD and LOQ values were 0.02 and 0.05 ng mL−1, respectively, whereas MDL and MQL values in real water samples (river water, groundwater, well water, and wastewater) were lower than 0.05 and 0.2 ng mL−1, respectively.Eight photodegradation products were identified, among which five for the first time. Based on the MS and MS/MS fragmentation, the chemical structures of the degradation products were proposed. Hydrolysis experiments were carried out on the same solutions preserved in the dark, but no formation of other species was highlighted.The method was applied to several real samples: CPT-11 was detected and quantified only in a hospital effluent sample at the concentration of 0.41 ± 0.2 ng mL−1 together with the occurrence of PDP3.The outcomes of this study may be useful for updating the pollutant screening in water samples.

A compound system involving three matrices (water, sediment, and paddy soil) was conceived to determine the potential sources of metal(loid)s (Ti, Fe, Co, Ni, Cu, Zn, As, Cd, Pb, and U) and synthetically evaluate their pollution levels in the Le’an River basin. The result indicated that the established background values (BVs) of paddy soil and sediment in the compound system were obviously higher than those of the upper continental crust (UCC) and soils from Jiangxi Province, a difference which was especially marked for sediment. The concentrations of Cu, Zn, As, Cd in the system had high coefficients of variation (CVs), and metal(loid)s in sediment showed higher levels than those in paddy soil, except for Pb. Cd and Cu in the system had the highest Ef levels, which probably pose a high risk to organisms and the health of local residents. There were significantly linear relationships between the site rank index (SRI) for water and that for sediment or paddy soil, revealing that matrices in the system interacted with each other. Principal component analysis (PCA) and absolute principal component scores and multiple linear regression model (APCS-MLR) results demonstrated that Cu, Zn, As, Cu, Pb, and U enrichments in the system were mainly affected by mining activities and were predominately deposited in sediment. Point pollution sources rather than non-point pollution sources such as mining activities, contributed most of the anthropogenic metal(loid)s to sediment. Both SRI and Hierarchical cluster analysis (HCA) results visually showed that S5, S8, S9, S10, S11, and S12 severe pollution grouped together and scattered through areas with extensive mining activities, while other sites with moderate pollution were spread along the main stream of the Le’an River.

Fungi have an exceptional capability to flourish in presence of heavy metals and pesticide. However, the mechanism of bioremediation of pesticide (lindane) and multimetal [mixture of cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), zinc (Zn)] by a fungus is little understood. In the present study, Aspergillus fumigatus, a filamentous fungus was found to accumulate heavy metals in the order [Zn(98%)>Pb(95%)>Cd(63%)>Cr(62%)>Ni(46%)>Cu(37%)] from a cocktail of 30 mg L⁻¹ multimetal and lindane (30 mg L⁻¹) in a composite media amended with 1% glucose. Particularly, Pb and Zn uptake was enhanced in presence of lindane. Remarkably, lindane was degraded to 1.92 ± 0.01 mg L⁻¹ in 72 h which is below the permissible limit value (2.0 mg L⁻¹) for the discharge of lindane into the aquatic bodies as prescribed by European Community legislation. The utilization of lindane as a cometabolite from the complex environment was evident by the phenomenal growth of the fungal pellet biomass (5.89 ± 0.03 g L⁻¹) at 72 h with cube root growth constant of fungus (0.0211 g¹/³ L⁻¹/³ h⁻¹) compared to the biomasses obtained in case of the biotic control as well as in presence of multimetal complex without lindane. The different analytical techniques revealed the various stress coping strategies adopted by A. fumigatus for multimetal uptake in the simultaneous presence of multimetal and pesticide. From the Transmission electron microscope coupled energy dispersive X-ray analysis (TEM-EDAX) results, uptake of the metals Cd, Cu and Pb in the cytoplasmic membrane and the accumulation of the metals Cr, Ni and Zn in the cytoplasm of the fungus were deduced. Fourier-transform infrared spectroscopy (FTIR) revealed involvement of carboxyl/amide group of fungal cell wall in metal chelation. Thus A. fumigatus exhibited biosorption and bioaccumulation as the mechanisms involved in detoxification of multimetals.

The increasing content of platinum group metal particles emitted into the environment by car traffic is gradually attracting the attention of the scientific community. However, the methods for the determination of platinum group metals in environmental matrices are either costly or suffer from low sensitivity. To facilitate the use of less sensitive, but significantly cheaper, devices, the preconcentration of platinum group metals is employed. For platinum, a multitude of preconcentration approaches have been published. On the contrary, the preconcentration approaches for palladium are still rare. In this work, the development, optimization, and testing of a new approach is described; it is based on a preconcentration of palladium on octadecyl modified silica gel together with the complexing agent dimethylglyoxime, and it is then analyzed with the high-resolution continuum-source atomic absorption spectrometry. For comparison, a newly developed sorbent, QuadraSil™ TA, with a high affinity for platinum group metals was also tested. The preconcentraiton approach was tested on the lichen Hypogymnia physodes, which served as a bioindicator of palladium emissions. The case study site was a mid-sized city in central Europe: Brno, Czech Republic. The dry “bag” monitoring technique was used to collect the palladium near roads with a large span of traffic density. The developed analytical approach confirmed an increasing concentration of palladium with increasing exposure time and intensity of the traffic. Consequently, a simple relationship between the amount of bioaccumulated palladium and traffic density was established.

Stibnite (Sb₂S₃) dissolution and transformation on mineral surfaces are the fundamental steps controlling the fate of antimony (Sb) in the environment. The molecular-level understanding of Sb₂S₃-mineral-water interfacial reactions is of great importance. Herein, Sb₂S₃ oxidative dissolution and sequestration on pyrite (FeS₂) were explored. The results show that FeS₂ accelerated the rate of Sb₂S₃ oxidative dissolution by a factor of 11.4-fold under sunlight due to heterogeneous electron transfer. The electron transfer from Sb₂S₃ to FeS₂ separated photogenerated hole (h⁺) and electron (e⁻) pairs, facilitating the generation of hydroxyl radicals (OH) on Sb₂S₃ and FeS₂, and superoxide radicals (O₂⁻) on FeS₂. Surface O₂⁻ was the dominant oxidant for Sb(III) oxidation with 91% contribution, as evidenced by radical trapping experiments. OH was preferentially adsorbed on Sb₂S₃, but was released with Sb₂S₃ dissolution, and subsequently contributable to Sb(III) oxidation in solution. The Sb(III) oxidation and sequestration on FeS₂ surface coupled Fe²⁺/Fe³⁺ cycling and inhibited FeS₂ dissolution, as evidenced by X-ray absorption near edge structure and X-ray photoelectron spectroscopy. The insights gained from this study further our understanding of Sb₂S₃ transformation and transport at the environmental mineral-water interfaces.