Sewage sludge from a municipal wastewater treatment facility employing activated sludge process was pre-incubated with varying substrates and mixtures of substrates including metformin (MET), guanylurea (GUA) and glucose. The biomass from enriched cultures separately utilising MET and glucose/GUA was then used to investigate the kinetics of aerobic biodegradation of MET and GUA, respectively, as individual substrates in batch reactors. The results showed that GUA can be completely degraded as a nitrogen source when glucose is provided as a carbon and energy source. On the contrary, MET can be biodegraded as a sole carbon and energy source. However, formation of by-product GUA in solution, which acts as a nitrogen source, rapidly increased the degradation rate of MET resembling autocatalytic behaviour. At low starting concentration of 5 mg/L, the specific substrate utilisation rates of MET and GUA were 0.0033 day⁻¹ and 0.0013 day⁻¹, respectively, which is reported first time in this study. Out of the five biodegradation kinetic models used to describe substrate utilisation, the Quiroga-Sales-Romero (QSR) model was found to predict the measured MET and GUA degradation profile well supported by the goodness of fit parameters. Furthermore, the QSR model was able to describe the autocatalytic degradation of MET and the incomplete biodegradation of GUA in solution.

Due to the activities inherent to medical care units, the hospital effluent released contains diverse contaminants such as tensoactives, disinfectants, metals, pharmaceutical products and chemical reagents, which are potentially toxic to the environment since they receive no treatment or are not effectively removed by such treatment before entering the drain. They are incorporated into municipal wastewater, eventually entering water bodies where they can have harmful effects on organisms and can result in ecological damage. To determine the toxicological risk induced by this type of eflluents, eight metals and 11 pharmaceuticals were quantified, in effluent from a hospital. Developmental effects, teratogenesis and oxidative stress induction were evaluated in two bioindicator species: Xenopus laevis and Lithobates catesbeianus. FETAX (frog embryo teratogenesis assay–Xenopus) was used to obtain the median lethal concentration (LC50), effective concentration inducing 50% malformation (EC50), teratogenic index (TI), minimum concentration to inhibit growth (MCIG), and the types of malformation induced. Twenty oocytes in midblastula transition were exposed to six concentrations of effluent (0.1, 0.3, 0.5, 0.7, 0.9, 1%) and negative and positive (6-aminonicotinamide) controls. After 96 h of exposure, diverse biomarkers of oxidative damage were evaluated: hydroperoxide content, lipid peroxidation, protein carbonyl content, and the antioxidant enzymes superoxide dismutase and catalase. TI was 3.8 in X. laevis and 4.0 in L. catesbeianus, both exceed the value in the FETAX protocol (1.2), indicating that this effluent is teratogenic to both species. Growth inhibition was induced as well as diverse malformation including microcephaly, cardiac and facial edema, eye malformations, and notochord, tail, fin and gut damage. Significant differences relative to the control group were observed in both species with all biomarkers. This hospital effluent contains contaminants which represents a toxic risk, since these substances are teratogenic to the bioindicators used. The mechanism of damage induction may be associated with oxidative stress.

Venlafaxine is an antidepressant and anti-anxiety drug that has been detected in municipal wastewater at low μg/L concentrations. In this study, the nest-defense behavior of adult male fathead minnows (Pimephales promelas) was observed in fish exposed for a full lifecycle to venlafaxine nominal concentrations of 0.88, 8.8, and 88 μg/L (i.e. 1, 9.3, 75 μg/L mean measured concentrations). Nest-defense behaviors quantified were the time taken to contact a dummy intruder fish (on a flexible stick, held near each nest) and the number of contacts made during a 1 min period. In male fathead minnows exposed to venlafaxine over a full lifecycle at environmentally relevant nominal concentrations (i.e. 0.88 and 8.8 μg/L) no significant effects were observed in behavior. However, in males exposed over a full lifecycle to the highest concentration of venlafaxine (i.e. 88 μg/L), nest-defense behaviors were increased in males with empty nests, as shown by the significantly elevated percentage of empty-nest males that made contact with the dummy intruder fish (89%) relative to the lower percentage of contacts (65%) among the Control males (p = 0.046). Lifecycle exposure to high venlafaxine (88 μg/L) caused males to over-protect their empty nests. Environmental venlafaxine concentrations are approximately 70 x lower than this, so it is unlikely that behavioral changes from venlafaxine exposure would occur in the environment. Normal nest defense behaviours in control males varied, depending on whether they were protecting empty nests or nests with eggs. Compared to Control males with empty nests, more Control males with eggs in their nests made contact with the dummy intruder fish (p = 0.014), contact was faster (i.e. <10 s, p = 0.011), and they hit the dummy intruder fish more times in 1 min (p = 0.031) This study is the first to assess reproductive behaviors in fish exposed to an antidepressant over a full lifecycle.

Pharmaceutically active compounds (PhACs) are excreted by humans and animals and released into the aquatic environment through wastewater, which can have potential negative impacts on ecological systems. To conduct a nationwide investigation of the occurrence of PhACs in water resources in China, an analytical procedure based on solid-phase extraction (SPE) and LC-MS/MS was used to measure 45 PhACs in surface water samples from a network of 29 rivers across 31 provinces in China in 2014 and 2015. PhACs were prevalent in all sampled streams. The concentrations of commonly detected PhACs were comparable to those detected in other countries. High total concentrations (mean > 1 μg L−1) of all tested PhACs were primarily detected in areas under extreme water stress, specifically northern and eastern coastal areas. Source apportionment based on the profiles of the target compounds found that 54% of the PhACs in China originated from freshly discharged untreated sewage. Metformin (MET) and its biodegradation product, guanylurea (GUL), were used as a pair of indicators to predict PhAC contamination levels and differentiate between biotreated and unbiotreated wastewater. High MET/GUL can be used to indicate untreated wastewater, whereas low MET/GUL values are a strong indicator of treated wastewater. Furthermore, wastewater biotreatment ratios were calculated. We estimated that the biotreatment ratios of most of the provinces in China were less than 50%. We conclude that more attention should be paid to untreated sewage water, especially water in rural areas rather than the existing concentration on urban sewage treatment-oriented management.

Unknown compounds with (anti-)androgenic activities enter the aquatic environment via municipal wastewater treatment plants (WWTPs). Progestins are well-known environmental contaminants capable of interfering with androgen receptor (AR) signaling pathway. The aim of the present study was to determine if 15 selected progestins have potential to contribute to (anti-)androgenic activities in municipal wastewaters and the respective recipient surface waters. AR-specific Chemically Activated LUciferase gene eXpression bioassay in agonistic (AR-CALUX) and antagonistic (anti-AR-CALUX) modes and liquid chromatography tandem atmospheric pressure chemical ionization/atmospheric photoionization with hybrid quadrupole/orbital trap mass spectrometry operated in high resolution product scan mode (LC-APCI/APPI-HRPS) methods were used to assess (anti-)androgenic activity and to detect the target compounds, respectively. The contribution of progestins to (anti-)androgenic activities was evaluated by means of a biologically and chemically derived toxicity equivalent approach. Androgenic (0.08–59 ng/L dihydrotestosterone equivalents – DHT EQs) and anti-androgenic (2.4–26 μg/L flutamide equivalents – FLU EQs) activities and progestins (0.19–75 ng/L) were detected in selected aquatic environments. Progestins displayed androgenic potencies (0.01–0.22 fold of dihydrotestosterone) and strong anti-androgenic potencies (9–62 fold of flutamide). Although they accounted to some extent for androgenic (0.3–29%) and anti-androgenic (4.6–27%) activities in influents, the progestins’ contribution to (anti-)androgenic activities was negligible (≤2.1%) in effluents and surface waters. We also tested joint effect of equimolar mixtures of target compounds and the results indicate that compounds interact in an additive manner. Even if progestins possess relatively strong (anti-)androgenic activities, when considering their low concentrations (sub-ng/L to ng/L) it seems unlikely that they would be the drivers of (anti-)androgenic effects in Czech aquatic environments.

Carbendazim is a fungicide commonly used as active substance in plant protection products and biocidal products, for instance to protect facades of buildings against fungi. However, the subsequent occurrence of this fungicide and potential endocrine disruptor in the aqueous environment is a major concern. In this study, high resolution mass spectrometry shows that carbendazim can be detected with an increasing abundance from the source to the mouth of the River Rhine. Unexpectedly, the abundance of carbendazim correlates poorly with that of other fungicides used as active ingredients in plant protection products (r² of 0.32 for cyproconazole and r² of 0.57 for propiconazole) but it correlates linearly with that of pharmaceuticals (r² of 0.86 for carbamazepine and r² of 0.89 for lamotrigine). These results suggest that the occurrence of carbendazim in surface water comes mainly from the discharge of treated domestic wastewater. This hypothesis is further confirmed by the detection of carbendazim in wastewater effluents (n = 22). In fact, bench-scale leaching tests of textiles and papers revealed that these materials commonly found in households could be a source of carbendazim in domestic wastewater. Moreover, additional river samples collected nearby two paper industries indicate that the discharge of their treated process effluents is also a source of carbendazim in the environment. While characterizing paper and textile as overlooked sources of carbendazim, this study also shows the biocide as a possible ubiquitous wastewater contaminant that would require further systematic and worldwide monitoring due to its toxicological properties.

Municipal wastewater treatment plants (WWTPs) are important in the migration and transformation of perfluoroalkyl substances (PFASs) in water bodies. Six municipal WWTPs located in the upper reaches of the Guanting reservoir, along the Yanghe River, were sampled from November 2016 to July 2017. Influents, effluents, and activated sludge solutions were sampled and the concentrations of 17 PFASs were analyzed. Perfluorobutanoic acid (PFBA), Perfluorooctanoic acid (PFOA), Perfluorohexanoic acid (PFHxA), Perfluoropentanoic acid (PFPeA), Perfluorobutane sulfonat (PFBS) and Perfluorooctane sulfonate (PFOS) accounted for more than 90% of these. Seasonal variations in PFASs in influent directly influenced concentrations in supernatant and effluent. The annual average PFAS concentrations were 46.4, 45.1, and 38.5 ng L⁻¹ in influent, supernatant, and effluent, respectively, indicating that WWTPs do not efficiently remove PFASs from wastewater. Annual average PFAS removal efficiencies differed among WWTPs, were influenced primarily by the treatment process used at each, and followed the order Cyclic Activated Sludge System (CASS, 32.2%) > Orbal Oxidation Ditch (OD, 17.5%) > Anaeroxic–Anoxic–Oxic (A²/O, −1.49%). Short-chain PFASs were removed significantly more efficiently in the CASS compared to the other systems. These results can show how traditional wastewater treatment plants can help remove PFASs from the environment.

Plastic pollution in the environment is currently receiving worldwide attention. Improper dumping of disused or abandoned plastic wastes leads to contamination of the environment. In particular, the disposal of municipal wastewater effluent, sewage sludge landfill, and plastic mulch from agricultural activities is a serious issue and of major concern regarding soil pollution. Compared to plastic pollution in the marine and freshwater ecosystems, that in the soil ecosystem has been relatively neglected. In this study, we discussed plastic pollution in the soil environment and investigated research on the effects of plastic wastes, especially microplastics, on the soil ecosystem. We found that earthworms have been predominantly used as the test species in investigating the effects of soil plastic pollution on organisms. Therefore, further research investigating the effects of plastic on other species models (invertebrates, plants, microorganisms, and insects) are required to understand the effects of plastic pollution on the overall soil ecosystem. In addition, we suggest other perspectives for future studies on plastic pollution and soil ecotoxicity of plastics wastes, providing a direction for such research.

In this work we have investigated in details the process of degradation of the 4-amino-6-chlorobenzene-1,3-disulfonamide (ABSA), stable hydrolysis product of frequently used pharmaceutical hydrochlorothiazide (HCTZ), as one of the most ubiquitous contaminants in the sewage water. The study encompassed investigation of degradation by hydrolysis, photolysis, and photocatalysis employing commercially available TiO₂ Degussa P25 catalyst. The process of direct photolysis and photocatalytic degradation were investigated under different type of lights. Detailed insights into the reactive properties of HCTZ and ABSA have been obtained by density functional theory calculations and molecular dynamics simulations. Specifically, preference of HCTZ towards hydrolysis was confirmed experimentally and explained using computational study. Results obtained in this study indicate very limited efficiency of hydrolytic and photolytic degradation in the case of ABSA, while photocatalytic degradation demonstrated great potential. Namely, after 240 min of photocatalytic degradation, 65% of ABSA was mineralizated in water/TiO₂ suspension under SSI, while the nitrogen was predominantly present as NH4+. Reaction intermediates were studied and a number of them were detected using LC-ESI-MS/MS. This study also involves toxicity assessment of HCTZ, ABSA, and their mixtures formed during the degradation processes towards mammalian cell lines (rat hepatoma, H-4-II-E, human colon adenocarcinoma, HT-29, and human fetal lung, MRC-5). Toxicity assessments showed that intermediates formed during the process of photocatalysis exerted only mild cell growth effects in selected cell lines, while direct photolysis did not affect cell growth.

There is less research on the hydrological system and its destruction processes mechanism in the mining areas, especially combined application of isotope technology and chemical signals, which is a key scientific problem that need to be solved. This study takes Jinci spring area in Shanxi as a case study. It is based on the data of hydrology and mining condition from 1954 to 2015, combining monitoring experiments, O18, D, S34 and N15 tracing, chemical and model simulation. This study investigates the hydrological regularity and impacts of mining activities on water quantity and quality, and reveals the destruction process of hydrological system. The results show that: (1) Water chemical type shows an evolutionary trend of HCO3−-Ca2+-Mg2+→SO42--HCO3--Ca2+-Mg2+→SO42--Ca2+-Mg2+, due to the influence of exploitation and fault zones. Isotope tracer shows that mine pit water is formed by a mixture of pore water, karst water and surface water. (2) Although precipitation and seepage have a certain impact on the reducing of groundwater quantity, over-exploitation of water resource is still the main reason for reducing of groundwater quantity. Under the conditions of keeping the exploitation intensity at the current level or reducing it by 10%, groundwater level shows a declining trend. Under the condition of reducing it by 30%, groundwater level starts to rise up. When reducing by 50%, groundwater level reaches its highest point. Coalmining changes the runoff, recharge and discharge paths. (3) From 1985 to 2015, Water quality in the mining area is worsening. Ca2+ increases by 35.30%, SO42− increases by 52.80%, and TDS (Total Dissolved Solid) increases by 67.50%. Nitrates come from the industrial and domestic wastewater, which is generated by mining. The percentage of groundwater coming from gypsum dissolusion is 67.51%, and the percentage from coal measure strata water is 34.49%. The water qualities of river branches are generally deteriorated.