Oceanic oil spills present significant ecological risks that have the potential to contaminate extensive areas, including coastal regions. The occurrence of the 2019 oil spill event in Brazil resulted in over 3000 km of contaminated beaches and shorelines. While assessing the impact on benthic and beach ecosystems is relatively straightforward due to direct accessibility, evaluating the ecotoxicological effects of open ocean oil spills on the pelagic community is a complex task. Difficulties are associated with the logistical challenges of responding promptly and, in case of the Brazilian mysterious oil spill, to the subsurface propagation of the oil that impeded remote visual detection. An oceanographic expedition was conducted in order to detect and evaluate the impact of this oil spill event along the north-eastern Brazilian continental shelf. The pursuit of dissolved and dispersed oil compounds was accomplished by standard oceanographic methods including seawater polycyclic aromatic hydrocarbons (PAHs) analysis, biomass stable carbon isotope (δ13C), particulate organic carbon to particulate organic nitrogen (POC:PON) ratios, nutrient analysis and ecotoxicological bioassays using the naupliar phase of the copepod Tisbe biminiensis. Significant ecotoxicological effects, reducing naupliar development by 20-40 %, were indicated to be caused by the presence of dispersed oil in the open ocean. The heterogeneous distribution of oil droplets aggravated the direct detection and biochemical indicators for oil are presented and discussed. Our findings serve as a case study for identifying and tracing subsurface propagation of oil, demonstrating the feasibility of utilizing standard oceanographic and ecotoxicological methods to assess the impacts of oil spill events in the open ocean. Ultimately, it encourages the establishment of appropriate measures and responses regarding the liability and regulation of entities to be held accountable for oil spills in the marine environment.

This work proposes an approach to the formation of receptor elements for the rapid diagnosis of the state of surface waters according to two indicators: the biochemical oxygen demand (BOD) index and toxicity. Associations among microorganisms based on the bacteria P. yeei and yeast S. cerevisiae, as well as associations of the yeasts O. polymorpha and B. adeninivorans, were formed to evaluate these indicators, respectively. The use of nanocomposite electrically conductive materials based on carbon nanotubes, biocompatible natural polymers-chitosan and bovine serum albumin cross-linked with ferrocenecarboxaldehyde, neutral red, safranin, and phenosafranin-has made it possible to expand the analytical capabilities of receptor systems. Redox polymers were studied by IR spectroscopy and Raman spectroscopy, the contents of electroactive components were determined by atomic absorption spectroscopy, and electrochemical properties were studied by electrochemical impedance and cyclic voltammetry methods. Based on the proposed kinetic approach to modeling individual stages of bioelectrochemical processes, the chitosan-neutral red/CNT composite was chosen to immobilize the yeast association between O. polymorpha (ks = 370 ± 20 L/g × s) and B. adeninivorans (320 ± 30 L/g × s), and a bovine serum albumin (BSA)-neutral composite was chosen to immobilize the association between the yeast S. cerevisiae (ks = 130 ± 10 L/g × s) and the bacteria P. yeei red/CNT (170 ± 30 L/g × s). After optimizing the composition of the receptor systems, it was shown that the use of nanocomposite materials together with associations among microorganisms makes it possible to determine BOD with high sensitivity (with a lower limit of 0.6 mg/dm3) and detect the presence of a wide range of toxicants of both organic and inorganic origin. Both receptor elements were tested on water samples, showing a high correlation between the results of biosensor analysis of BOD and toxicity and the results of standard analytical methods. The results obtained show broad prospects for creating sensitive and portable bioelectrochemical sensors for the early warning of environmentally hazardous situations based on associations among microorganisms and nanocomposite materials.

Water toxicity, one of the major concerns for ecosystems and the health of humanity, is usually attributed to inorganic anions-induced contamination. Particularly, cyanide ions are considered one of the most harmful elements required to be monitored in water. The need for cyanide sensing and monitoring has tempted the development of sensing technologies without highly sophisticated instruments or highly skilled operations for the objective of in-situ monitoring. Recent decades have witnessed the growth of noble metal nanomaterials-based sensors for detecting cyanide ions quantitatively as nanoscience and nanotechnologies advance to allow nanoscale-inherent physicochemical properties to be exploited for sensing performance. Particularly, noble metal nanostructure e-based optical sensors have permitted cyanide ions of nanomolar levels, or even lower, to be detectable. This capability lends itself to analytical application in the quantitative detection of harmful elements in environmental water samples. This review covers the noble metal nanomaterials-based sensors for cyanide ions detection developed in a variety of approaches, such as those based on colorimetry, fluorescence, Rayleigh scattering (RS), and surface-enhanced Raman scattering (SERS). Additionally, major challenges associated with these nano-platforms are also addressed, while future perspectives are given with directions towards resolving these issues.

Our previous studies have reported water toxicity determination with a fresh electrochemically active bacteria (EAB) suspension as the sensing element, which exhibits high sensitivity and has great prospects in providing early warning about water pollution. However, because the preparation of fresh EAB suspensions is time-consuming, these studies are not suitable for the on-site determination of water toxicity. To solve this problem, this study investigated the rapid preparation of an EAB suspension by the rehydration of freeze-dried EABs and established a novel method for the on-site determination of water toxicity based on the freeze-dried EAB model strain Shewanella oneidensis MR-1. The results demonstrate that the optimal cryoprotectant for S. oneidensis MR-1 freeze drying is 7.5 % (w/v) skimmed milk powder. Compared with fresh S. oneidensis MR-1, freeze-dried S. oneidensis MR-1 exhibits similar extracellular electron transfer (EET) performance (74.7 % ± 0.3 %) and slightly lower sensitivity for water toxicity determination (65.8 % ± 2.2 %) with the optimal cryoprotectant. On-site determination of water toxicity was realized by using freeze-dried S. oneidensis MR-1, and the detection limits of five common toxic pollutants (Cd2+, Pb2+, Cu2+, phenol and dichlorophenol) reached 0.5 mg/L. Water toxicity determination is capable of resisting common interferences, e.g., glucose, lactate, nitrate and nitrite, and shows high accuracy in practical applications.

Microbial mediator biosensors for surface water toxicity determination make it possible to carry out an early assessment of the environmental object’s quality without time-consuming standard procedures based on standard test-organisms, and provide broad opportunities for receptor element modifying depending on the required operational parameters analyzer. Four microorganisms with broad substrate specificity and nine electron acceptors were used to form a receptor system for toxicity assessment. Ferrocene was the most effective mediator according to its high rate constant of interaction with the microorganisms (0.33 ± 0.01 dm3/(g × s) for yeast Saccharomyces cerevisiae). Biosensors were tested on samples containing four heavy metal ions (Cu2+, Zn2+, Pb2+, Cd2+), two phenols (phenol and p-nitrophenol), and three natural water samples. The «ferrocene- Escherichia coli» and «ferrocene-Paracoccus yeei, E. coli association» systems showed good operational stability with a relative standard deviation of 6.9 and 7.3% (14 measurements) and a reproducibility of 7 and 5.2% using copper (II) ions as a reference toxicant. Biosensor analysis with these systems was shown to highly correlate with the results of the standard method using Chlorella algae as a test object. Developed biosensors allow for a valuation of the polluted natural water’s impact on the ecosystem via an assessment of the influence on bacteria and yeast in the receptor system. The systems could be used in toxicological monitoring of natural waters.

This study reports for the first-time the possibility of deploying gas production by thiosulfate utilizing denitrifying bacteria (TUDB) as a proxy to evaluate water toxicity. The test relies on gas production by TUDB due to inhibited metabolic activity in the presence of toxicants. Gas production was measured using a bubble-type respirometer. Optimization studies indicated that 300 mg NO3--N/L, 0.5 mL acclimated culture, and 2100 mg S2O32-/L were the ideal conditions facilitating the necessary volume of gas production for sensitive data generation. Determined EC50 values of the selected heavy metals were: Cr6+, 0.51 mg/L; Ag+, 2.90 mg/L; Cu2+, 2.90 mg/L; Ni2+, 3.60 mg/L; As3+, 4.10 mg/L; Cd2+, 5.56 mg/L; Hg2+, 8.06 mg/L; and Pb2+, 19.3 mg/L. The advantages of this method include operational simplicity through the elimination of cumbersome preprocessing procedures which are used to eliminate interferences caused by turbidity when the toxicity of turbid samples is determined via spectrophotometry.

To determine whether the marine medaka Oryzias melastigma is a suitable model organism for in vivo acute toxicity bioassay in seawater, we first determined whether there were differences in the concentrations of chemicals that were toxic to marine medaka (O. melastigma) and freshwater medaka (O. latipes). We performed in vivo acute toxicity bioassay with 3-chloroaniline, triclosan, 3,4-dichloroaniline, fenitrothion, and pyriproxyfen on larvae of both species. Although the concentrations of 3-chloroaniline and fenitrothion that were lethal to the larvae were identical for both species, the toxic concentrations of triclosan, 3,4-dichloroaniline, and pyriproxyfen were lower for O. melastigma than for O. latipes. We then used an in vivo acute toxicity bioassay to monitor the quality of coastal seawater in Akita, Japan. No lethal effects were observed in the harbor and canal in 2019. O. melastigma could be used to monitor the quality of seawater with salinities in the range 2-25. Our findings suggest that O. melastigma can be used as the test fish for in vivo acute toxicity bioassay intended for water quality monitoring.

The development of tools to monitor water quality is mandatory in a scenario where clean water resources are decreasing. Here, the biosensing capability of an electroactive river sediment consortium was tested towards three model contaminants (glutaraldehyde, nickel(II) and chromium(III)). The proposed biosensor is a small membrane-less single chamber Microbial Fuel Cell (MFC), fabricated by 3D printing. Its semi-continuous mode of operation resulted in long-term current profile stability and reproducibility. A linear trend of response was obtained for glutaraldehyde in a concentration range of 5-1000 ppm. After the recovery of the electroactive consortium activity, the MFC-based biosensors were shown to be sensitive towards Ni(II) and Cr(III), at concentrations above 2 mg L-1. To effectively analyze biosensor response, a novel algorithm was proposed, offering advantages for the realization of energy-saving protocols for MFC-biosensor data transmission. Implementation of the device and method, from laboratory test to real environment, can offer a low cost in situ system for detection of water contaminants.

The removal of bromide (Br-) and iodide (I-) from source waters mitigates the formation of brominated and iodinated disinfection by-products (DBPs), which are more toxic than their chlorinated analogues. In this study, we report on our recently developed environmental-friendly method for the preparation of novel silver chloride/superfine activated carbon composite (AgCl-SPAC) to rapidly and selectively remove Br- and I- from surface waters. The material characteristics were tracked, before and after treatment, using scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), X-ray diffraction (XRD), and X-ray photoelectron spectra (XPS) spectroscopies. The results showed very fast removal kinetics of Br- and I- by AgCl-SPAC with equilibrium times at 150 s and <10 s, respectively (i.e., 2-3 orders of magnitudes faster than previously tested Ag-based composites). In addition, AgCl-SPAC was evaluated under eight different Cl- concentrations up to 400 mg/L and exhibited high removal efficiencies for I- (i.e., >90% at all tested conditions) and Br- (i.e, >80% at Cl- = 0.5-200 mg/L, and 60-75% at extreme Cl- conditions = 300-400 mg/L). Unlike previous Ag-based composites, AgCl-SPAC performance was not affected by elevated concentrations of two types of natural organic matter (2-16 mg-NOM/L). The superior performance was further confirmed in four different surface waters and one groundwater. After the removal of Br- and I- from all waters by AgCl-SPAC, the subsequent DBPs formation (trihalomethanes, haloacetic acids, and haloacetonitriles), total organic halogens (TOX), bromine substitution factor (BSF), and calculated cytotoxicity under the uniform formation conditions (UFC) decreased significantly. Overall, this novel composite represents a promising alternative approach, to be integrated continuously or seasonally, for controlling the formation of brominated and/or iodinated DBPs at water treatment plants.

The industrial wastes, sewage effluents, agricultural run-off and decomposition of biological waste may cause high environmental concentration of chemicals that can interfere with the cell cycle activating the programmed process of cells death (apoptosis). In order to provide a detailed understanding of environmental pollutants-induced apoptosis, here we reviewed the current knowledge on the interactions of environmental chemicals and programmed cell death. Metals (aluminum, arsenic, cadmium, chromium, cobalt, zinc, copper, mercury and silver) as well as other chemicals including bleached kraft pulp mill effluent (BKME), persistent organic pollutants (POPs), and pesticides (organo-phosphated, organo-chlorinated, carbamates, phyretroids and biopesticides) were evaluated in relation to apoptotic pathways, heat shock proteins and metallothioneins. Although research performed over the past decades has improved our understanding of processes involved in apoptosis in fish, yet there is lack of knowledge on associations between environmental pollutants and apoptosis. Thus, this review could be useful tool to study the cytotoxic/apoptotic effects of different pollutants in fish species.