Assessment of the impact of pharmaceutical residues on living organisms is a very complex subject. Apart from taking into account the toxicity of individual compounds, environmental factors should also be taken into account. In this paper, attempts were made to assess the impact of coexisting inorganic ions and changes in pH on the toxicity of ten selected pharmaceuticals. Two bioassays were used to measure the estrogenic and androgenic effects (XenoScreen YES/YAS – Saccharomyces cerevisiae) and acute toxicity (Microtox® – Vibrio fischeri).The Microtox® test gave the most definitive outputs concerning the determination of interaction type between drugs and chemical species. Synergism was proven for almost all drugs and chemical species, and only two cases of antagonism were found. Significant drug/pH interactions were rare.Regarding the XenoScreen YES/YAS bioassay, when estrogenic and androgenic agonistic effects (YES+ and YAS+, respectively) were studied, many cases of well-expressed synergism for all inorganic ions with limited number of drugs (diazepam, fluoxetine, estrone, chloramphenicol for the YES+ test and diazepam, progesterone, androstenedione, and estrone for the YAS+ test) were found. Antagonism was also proven for the YES+ test, especially for diclofenac and androstenedione interacting with cations. On the other hand, the YES- and YAS- tests (estrogenic and androgenic, respectively, antagonistic effects) did not indicate cases of synergetic interaction except for the couples Br−/diazepam and NH4+/ketoprofen. Antagonistic drug/ion interactions were detected only with diclofenac and fluoxetine. It is interesting that well-expressed (antagonism or synergism) drug/pH interactions were rare.Both tests were found utilizable in performing studies on impact of ions/pH fluctuations on drugs mixtures' toxicity confirming in most cases synergic impact of parameters studied on toxicity. The approach proposed in the paper seems to be proven as a reliable tool in assessing impact of abiotic factors on toxicity and endocrine potential of complex mixtures of pharmaceuticals' mixtures.

The mechanisms contributing to toxic effects of airborne lower-chlorinated PCB congeners (LC-PCBs) remain poorly characterized. We evaluated in vitro toxicities of environmental LC-PCBs found in both indoor and outdoor air (PCB 4, 8, 11, 18, 28 and 31), and selected hydroxylated metabolites of PCB 8, 11 and 18, using reporter gene assays, as well as other functional cellular bioassays. We focused on processes linked with endocrine disruption, tumor promotion and/or regulation of transcription factors controlling metabolism of both endogenous compounds and xenobiotics. The tested LC-PCBs were found to be mostly efficient anti-androgenic (within nanomolar – micromolar range) and estrogenic (at micromolar concentrations) compounds, as well as inhibitors of gap junctional intercellular communication (GJIC) at micromolar concentrations. PCB 8, 28 and 31 were found to partially inhibit the aryl hydrocarbon receptor (AhR)-mediated activity. The tested LC-PCBs were also partial constitutive androstane receptor (CAR) and pregnane X receptor (PXR) agonists, with PCB 4, 8 and 18 being the most active compounds. They were inactive towards other nuclear receptors, such as vitamin D receptor, thyroid receptor α, glucocorticoid receptor or peroxisome proliferator-activated receptor γ. We found that only PCB 8 contributed to generation of oxidative stress, while all tested LC-PCBs induced arachidonic acid release (albeit without further modulations of arachidonic acid metabolism) in human lung epithelial cells. Importantly, estrogenic effects of hydroxylated (OH-PCB) metabolites of LC-PCBs (4-OH-PCB 8, 4-OH-PCB 11 and 4′-OH-PCB 18) were higher than those of the parent PCBs, while their other toxic effects were only slightly altered or suppressed. This suggested that metabolism may alter toxicity profiles of LC-PCBs in a receptor-specific manner. In summary, anti-androgenic and estrogenic activities, acute inhibition of GJIC and suppression of the AhR-mediated activity were found to be the most relevant modes of action of airborne LC-PCBs, although they partially affected also additional cellular targets.

We evaluated the chronic impact of oxytetracycline (OTC) on performance and antibiotic resistance development during the mesophilic anaerobic digestion (AD) of antibiotic-containing biomass. Mesophilic AD was conducted in a completely stirred tank reactor by constantly feeding municipal excess sludge spiked with increasing concentrations of OTC (0–1000 mg L−1) under a solid retention time of 20 days over a period of 265 days. Results showed that methane generation of mesophilic AD was inhibited when the OTC concentration in digested sludge was increased to around 18,000 mg kg−1 (OTC dose, 1000 mg L−1), due to the inhibition of fermenting and acidogenic bacteria. Metagenomic sequencing and high-throughput quantitative PCR analysis demonstrated that tetracycline resistance genes were the most dominant type (38.47–43.76%) in the resistome, with tetG, tetX, tetM, tetR, tetQ, tetO, and tetL as the dominant resistant subtypes throughout the whole experimental period. The relative abundance of these tet genes increased from 2.10 × 10−1 before spiking OTC (OTC concentration in digested sludge, 8.97 mg kg−1) to 2.83 × 10−1 (p < 0.05) after spiking OTC at a dose of 40 mg L−1 (OTC concentration in digested sludge, 528.52 mg kg−1). Furthermore, mobile genetic elements, including integrons, transposons, and plasmids, were also enriched with the increase in OTC dose. Based on partial canonical correspondence analysis, the contributions of horizontal (mobile element alteration) and vertical (bacterial community shift) gene transfer to antibiotic resistome variation were 29.35% and 21.51%, respectively. Thus, considering the inhibition of hydrolytic acidification and enrichment of antibiotic resistome, mesophilic AD is not suggested to directly treat the biomass containing OTC concentration higher than 200 mg L−1.

Biochar-leached dissolved organic matter may have a substantial impact on the water quality of receiving water surrounded by biochar-amended fields. In this study, we tracked variations in the spectroscopic characteristics and the disinfection by-products formation potentials of dissolved organic matter (DOM) leached during sequential extraction for three different biochars (BCs), which simulates DOM from BC-amended fields during intermittent rain events. The optical properties of DOM were more dependent on the BC types with different origins (sludge, corn, and rice) rather than on the extraction time. A large amount of DOM was released during the initial period of the extraction (1 day), which was equivalent to 52–60% of the total cumulative organic carbon during 17 days of extraction. The relative contribution of the initial extraction to the total cumulative amounts was greater for the formation potential of trihalomethanes (THMs) per BC (71–82%) compared to those of haloacetic acids (HAAs) or dissolved organic carbon (DOC), suggesting that the leaching behaviors of disinfection byproducts (DBP) precursors from BCs may be different from those of DOC (i.e., bulk DOM). Among the three BCs, corn BC-derived DOM exhibited the highest formation potentials of THMs and HAAs per BC for both the initial and the total cumulative extraction. The specific (or DOC-normalized) THMs formation potential was positively correlated with the ratios of terrestrial humic-like to fulvic-like components, implying condensed aromatic structures could operate as a surrogate for THMs formation of BC-derived DOM. This study provided insight into dynamic leaching behaviors of DOM from BCs and the formation potentials for THMs and HAAs in BC-amended fields under intermittent rainfall.

It is widely understood that microplastics (MPs) are ubiquitous in the marine environment yet less is known about MP abundance in freshwater rivers, particularly those of the western United States. This study documents MP pollution along the Snake River (∼1735 km) and from its confluence with the Columbia River to the Pacific Ocean. Grab and plankton net samples (mesh size 100 μm) were collected from the top 25 cm of surface water every 80.5 river km. MPs were identified if they met visual criteria and were verified with the hot needle test. A small representative subset of MPs from the net samples (16.7%) were selected based on appearance for micro-Raman spectroscopy in effort to provide examples of polymer types found in this study. Seventy-five percent of grab samples and 92.8% of net samples contained MPs, with concentrations ranging from 0 to 5.405 MP L−1 and 0 to 0.014 MP L−1 (0 to 13.7 MP m−3), respectively. The majority of fragments, films and beads were between 100 μm and 333 μm. This study identifies potential hotspots of MP pollution along the Snake and Lower Columbia rivers and prioritizes areas where more intensive sampling is needed. Sites with low flow or those further down river had higher numbers and the top two hotspots were located in areas with low population density but high agricultural use. Monitoring MP abundance in freshwater systems is important for establishing baseline levels of MP pollution and can direct laboratory toxicology studies in using more environmentally relevant concentrations for a better indication of how MP pollution affects ecosystems.

Sediment samples, including 40 surface samples and 12 sediment cores, were collected from 52 stations of the Yangtze River Estuary (YRE) in 2015 and 2016. The 95% linear prediction intervals (LPI) and principal components analysis (PCA), were conducted to evaluate the metal sources and grain-size effect (GSE). The in situ physico-chemical properties of pH, Eh, DO, salinity, temperature and turbidity were combined to elucidate the relationships between environmental factors and the fate of heavy metals in the river-estuary-shelf system. This study indicates a decreasing trend of metals in sediments from the estuary towards the adjacent shelf and the river channel and that Zn, Cu and Cr are mainly derived from natural processes throughout the catchment, whereas Pb appears to have anthropogenic inputs via atmospheric deposition. Furthermore, considering the best fit regression lines between the concentrations of Al and heavy metals as well as the deficiencies of the conventional Celements/CAl method, we introduce an approach (Al-SN: Al-scope normalization) that can eliminate the GSE on heavy metals and be applied to other estuaries. After Al-scope normalization, the relatively constant levels of Zn, Cu and Cr that remain in sediments from the river channel to the estuary and shelf confirmed that the variation of grain size in sediments almost entirely explained the distribution patterns of sediment toxicity in the YRE, while the enrichment of Pb in estuarine sediments could be attributed to its chemical species and physico-chemical properties. The results further suggest that the relationship between grain size and spatial behavior of sediment pollutants should be given priority over the contamination assessment and provenance discrimination in estuarine or similar environments with complex sediment compositions.

Biochar, a natural sourced carbon-rich material, has been used commonly in particle shape for carbon sequestration, soil fertility and environmental remediation. Here, we report a facile approach to fabricate freestanding biochar composite membranes for the first time. Wood biochars pyrolyzed at 300 °C and 700 °C were blended with polyvinylidene fluoride (PVdF) in three percentages (10%, 30% and 50%) to construct membranes through thermal phase inversion process. The resultant biochar composite membranes possess high mechanical strength and porous structure with uniform distribution of biochar particles throughout the membrane surface and cross-section. The membrane pure water flux was increased with B300 content (4825–5411 ± 21 L m⁻² h⁻¹) and B700 content (5823–6895 ± 72 L m⁻² h⁻¹). The membranes with B300 were more hydrophilic with higher surface free energy (58.84–60.31 mJ m⁻²) in comparison to B700 (56.32–51.91 mJ m⁻²). The biochar composite membranes indicated promising adsorption capacities (47–187 mg g⁻¹) to Rhodamine B (RhB) dye. The biochar membranes also exhibited high retention (74–93%) for E. coli bacterial suspensions through filtration. After simple physical cleaning, both the adsorption and sieving capabilities of the biochar composite membranes could be effectively recovered. Synergistic mechanisms of biochar/PVdF in the composite membrane are proposed to elucidate the high performance of the membrane in pollutant management. The multifunctional biochar composite membrane not only effectively prevent the problems caused by directly using biochar particle as sorbent but also can be produced in large scale, indicating great potential for practical applications.

Emission of hazardous trace elements (HTEs) from energy production is receiving much attention due to concerns about the toxicity to the ecosystem and human health. This study presented new field measurement data on the HTEs partitioning behavior and size-segregated elemental compositions of gaseous particular matter (PM) generated from a commercial circulating fluidized bed (CFB) power plant. Mineralogical and morphological characteristics of combustion ash and PM2.5 (particle diameter less than 2.5 μm) were determined by X-ray diffractometer (XRD) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS). Functional groups alteration during CFB combustion was characterized by Fourier transform infrared spectroscopy (FTIR). The presence of aliphatic hydrogen at 2910 cm−1 and 2847 cm−1 in the PM2.5 suggested that the aliphatic carbon-rich volatiles were absorbed on the fine particles with large surface area. Fine fly ash (PM2.5) occurred as irregular glass particles or/and as unburned carbon. The typical irregular particles were mainly composed of Al-Si-Ca or Al-Si-Fe phases. The enrichment behavior of HTEs was determined for the airborne size-segregated particular matter. Elemental occurrences, combustion temperature, unburnt carbon, and limestone additives during CFB combustion were critical in the transformation behavior of HTEs. The total potentially mobile pollutants that exit the CFB power plant every year were estimated as follows: 0.22 tons of Cr, 0.12 tons of Co, 0.73 tons of Ni, 0.04 tons of As, 0.07 tons of Se, 3.95 kg of Cd, and 3.34 kg of Sb.

Reduced physical performance is an important feature of aging, and walking speed is a valid measure of physical performance and mobility in older adults. Previous epidemiological studies suggest that cadmium exposure, even at low environmental levels, may contribute to vascular, musculoskeletal, and cognitive dysfunction, which may all be associated with reductions in physical performance. To this end, we investigated the associations of blood and urine cadmium concentrations with walking speed in middle-aged and older adults in the U.S. general population. We studied U.S. adults from the National Health and Nutrition Examination Survey 1999 to 2002 who were ≥50 years of age, who had determinations of cadmium in blood or in urine, and who had measurements of the time taken to walk 20 feet. Walking speed (ft/sec) was computed as walked distance (20 ft) divided by measured time to walk (in seconds). The weighted geometric means of blood and urine cadmium were 0.49 [95% confidence interval (CI): 0.47, 0.52] μg/L and 0.37 (95% CI: 0.34, 0.42) ng/mL, respectively. After adjusting for sociodemographic, anthropometric, health-related behavioral, and clinical risk factors and inflammation markers, the highest (vs. lowest) quintile of blood cadmium was associated with a 0.18 (95% CI: 0.10, 0.25) ft/sec reduction in walking speed (p-Trend <0.001). No association was observed for urine cadmium levels with walking speed. Cadmium concentrations in blood, but not in urine, were associated with slower gait speed. Our findings add to the growing volume of evidence supporting cadmium's toxicity even at low levels of exposure.

A green alga, Chlamydomonas reinhardtii, was used to verify whether a simple Biotic Ligand Model (BLM) could be used to predict carefully controlled short-term biouptake for the lanthanide, Nd. In the absence of ligands or competitors, Nd biouptake was well described by a Michaelis-Menten equation with an affinity constant, KNd, of 10⁶.⁸ M⁻¹ and a maximum internalization flux of Jₘₐₓ = 1.70 × 10⁻¹⁴ mol cm⁻² s⁻¹. For bi-metal mixtures containing Nd and Ca, Mg, Sm or Eu, Nd uptake could also be well modelled by assigning experimentally determined affinity constants of KCₐ = 10².⁶ M⁻¹, KMg = 10³.⁴ M⁻¹, KSₘ = 10⁶.⁵ M⁻¹ and KEᵤ = 10⁶.⁵ M⁻¹. The similar values of Kₘ and Jₘₐₓ for the three rare earth elements (REEs): Sm, Eu and Nd is consistent with them sharing a common metal uptake site. On the other hand, in the presence of the small organic ligands (citric or malic acid), neither, free or total Nd concentrations could be used to quantitatively predict Nd internalization fluxes. In other words, in order to predict biouptake by simple BLM determinations, it was necessary to consider that the Nd complexes were bioavailable. The data strongly suggest that risk evaluations of the REE will require a new paradigm and new tools for evaluating bioavailability.