Decadal Assessment of Microplastics, Pharmaceuticals, and Pesticides as Contaminants of Emerging Concern in Kenya’s Surface Waters: A Review

Abstract

Studies investigating microplastics, pharmaceuticals, and pesticides as contaminants of emerging concern (CECs) in surface water sources in Kenya are reviewed. Contaminants of emerging concern are chemicals that have recently been discovered that may pose a threat to the environment, aquatic life, and human life. Microplastics in surface waters range from 1.56 to as high as 4520 particles/m3, with high concentrations recorded in coastal waters. The dominant microplastics are fibers, fragments, and films, with foams, granules, and pellets making up only a small percentage. The main source of pharmaceuticals in water sources is not wastewater-treatment plants but rather raw untreated sewage because high concentrations are found near informal settlements with poor sewage connectivity. Antibiotics are detected in the range of the limit of quantification to 320 μg/L, with sulfamethoxazole, trimethoprim, and ciprofloxacin being the most abundant antibiotics. The high frequency of detection is attributed to the general misuse of antibiotics in the country. A health risk assessment indicated that only ciprofloxacin and acetaminophen posed noncarcinogenic health risks in the Ndarugo River and Mombasa periurban creeks, respectively. Similarly, the detection of antiretroviral drugs, mainly lamivudine, nevirapine, and zidovudine, is associated with human immunodeficiency virus prevalence in Kenya. In the Lake Naivasha, Nairobi River, and Lake Victoria basins, frequently detected organochloride pesticides (OCPs) are methoxychlor, alachlor, endrin, dieldrin, endosulfan, endosulfan sulfate, α-hexachlorocyclohexane (α-HCH), γ-HCH, and dichlorodiphenyltrichloroethane (DDT), some of which occur above permissible concentrations. The presence of DDT in some sites translates to illegal use or historical application. The majority of individual OCPs posed no noncarcinogenic health risk, except dieldrin and aldrin which had a hazard quotient >1 in two sites. Therefore, more surveying and regular monitoring in different regions in Kenya concerning CECs is essential to determine the spatial variability and effective measures to be taken to reduce pollution. Environ Toxicol Chem 2023;42:2105–2118. © 2023 SETAC.

Lingering Effects of Legacy Industrial Pollution on Yellow Perch of the Detroit River

Lingering Effects of Legacy Industrial Pollution on Yellow Perch of the Detroit River

Stable isotope analysis at Trenton Channel, Detroit River, where polyaromatic hydrocarbon and polychlorinated biphenyl sediment contamination is highest, revealed trophic disruption compared with other sites in the Lake St. Clair–Detroit River system.


Abstract

We used yellow perch (Perca flavescens) captured at four sites differing in legacy industrial pollution in the Lake St. Clair–Detroit River system to evaluate the lingering sublethal effects of industrial pollution. We emphasized bioindicators of direct (toxicity) and indirect (chronic stress, impoverished food web) effects on somatic and organ-specific growth (brain, gut, liver, heart ventricle, gonad). Our results show that higher sediment levels of industrial contaminants at the most downstream Detroit River site (Trenton Channel) are associated with increased perch liver detoxification activity and liver size, reduced brain size, and reduced scale cortisol content. Trenton Channel also displayed food web disruption, where adult perch occupied lower trophic positions than forage fish. Somatic growth and relative gut size were lower in perch sampled at the reference site in Lake St. Clair (Mitchell's Bay), possibly because of increased competition for resources. Models used to determine the factors contributing to site differences in organ growth suggest that the lingering effects of industrial pollution are best explained by trophic disruption. Thus, bioindicators of fish trophic ecology may prove advantageous to assess the health of aquatic ecosystems. Environ Toxicol Chem 2023;42:2158–2170. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

AOP Report: Aryl Hydrocarbon Receptor Activation Leads to Early–Life Stage Mortality via Sox9 Repression‐Induced Craniofacial and Cardiac Malformations

Abstract

The aryl hydrocarbon receptors (Ahrs) are evolutionarily conserved ligand-dependent transcription factors that are activated by structurally diverse endogenous compounds as well as environmental chemicals such as polycyclic aromatic hydrocarbons and halogenated aromatic hydrocarbons. Activation of the Ahr leads to several transcriptional changes that can cause developmental toxicity resulting in mortality. Evidence was assembled and evaluated for two novel adverse outcome pathways (AOPs) which describe how Ahr activation (molecular initiating event) can lead to early–life stage mortality (adverse outcome), via either SOX9-mediated craniofacial malformations (AOP 455) or cardiovascular toxicity (AOP 456). Using a key event relationship (KER)-by-KER approach, we collected evidence using both a narrative search and a systematic review based on detailed search terms. Weight of evidence for each KER was assessed to inform overall confidence of the AOPs. The AOPs link to previous descriptions of Ahr activation and connect them to two novel key events (KEs), increase in slincR expression, a newly characterized long noncoding RNA with regulatory functions, and suppression of SOX9, a critical transcription factor implicated in chondrogenesis and cardiac development. In general, confidence levels for KERs ranged between medium and strong, with few inconsistencies, as well as several opportunities for future research identified. While the majority of KEs have only been demonstrated in zebrafish with 2,3,7,8-tetrachlorodibenzo-p-dioxin as an Ahr activator, evidence suggests that the two AOPs likely apply to most vertebrates and many Ahr-activating chemicals. Addition of the AOPs into the AOP-Wiki (https://aopwiki.org/) helps expand the growing Ahr-related AOP network to 19 individual AOPs, of which six are endorsed or in progress and the remaining 13 relatively underdeveloped. Environ Toxicol Chem 2023;42:2063–2077. © 2023 SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Analysis of a Passive Sampling Device to Assess the Behavior of Per‐ and Polyfluoroalkyl Substances in Sediments

Analysis of a Passive Sampling Device to Assess the Behavior of Per- and Polyfluoroalkyl Substances in Sediments

(A) A POCIS-based passive sampler accumulates PFAS in sediment pore water,and (B) PFAS uptake from sediments is described by an external mass transportmodel.


Abstract

Per- and polyfluoroalkyl substances (PFAS) are an emerging class of compounds that cause health and environmental problems worldwide. In aquatic environments, PFAS may bioaccumulate in sediment organisms, which can affect the health of organisms and ecosystems. As such, it is important to develop tools to understand their bioaccumulation potential. In the present study, the uptake of perfluorooctanoic acid (PFOA) and perfluorobutane sulfonic acid (PFBS) from sediments and water was assessed using a modified polar organic chemical integrative sampler (POCIS) as a passive sampler. While POCIS has previously been used to measure time-weighted concentrations of PFAS and other compounds in water, in our study, the design was adapted for analyzing contaminant uptake and porewater concentrations in sediments. The samplers were deployed into seven different tanks containing PFAS-spiked conditions and monitored over 28 days. One tank contained only water with PFOA and PFBS, three tanks contained soil with 4% organic matter, and three tanks contained soil combusted at 550 °C to minimize the influence of labile organic carbon. The uptake of PFAS from the water was consistent with previous research using a sampling rate model or simple linear uptake. For the samplers placed in the sediment, the uptake process was explained well using a mass transport based on the external resistance from the sediment layer. Uptake of PFOS in the samplers occurred faster than that of PFOA and was more rapid in the tanks containing the combusted soil. A small degree of competition was observed between the two compounds for the resin, although these effects are unlikely to be significant at environmentally relevant concentrations. The external mass transport model provides a mechanism to extend the POCIS design for measuring porewater concentrations and sampling releases from sediments. This approach may be useful for environmental regulators and stakeholders involved in PFAS remediation. Environ Toxicol Chem 2023;42:2171–2183. © 2023 SETAC

Analysis of Selenium in Fish Tissue: An Interlaboratory Study on Weight Constraints

Abstract

Environmental monitoring programs that target fish tissues for selenium (Se) analysis present unique sampling and analytical challenges. Selenium monitoring programs ideally focus on egg/ovary sampling but frequently sample multiple tissues with varying lipid content, often target small-bodied fish species because of their small home ranges, and require reporting in units of dry weight. In addition, there is a growing impetus for nonlethal tissue sampling in fish monitoring. As a result, Se monitoring programs often generate low-weight tissue samples of varying lipid content, which challenges analytical laboratories to quantify tissue Se concentrations accurately, precisely, and at desired detection limits. The objective of the present study was to stress-test some conventional analytical techniques used by commercial laboratories in terms of their ability to maintain data quality objectives (DQOs) in the face of sample weight constraints. Four laboratories analyzed blind a suite of identical samples, and data were compared against a priori DQOs for accuracy, precision, and sensitivity. Data quality tended to decrease with decreasing sample weight, particularly when samples were less than the minimum weights requested by the participating laboratories; however, effects of sample weight on data quality were not consistent among laboratories or tissue types. The present study has implications for accurately describing regulatory compliance in Se monitoring programs, highlighting some important considerations for achieving high data quality from low-weight samples. Environ Toxicol Chem 2023;42:2119–2129. © 2023 SETAC

Development of a Machine Learning Model to Estimate the Biotic Ligand Model–Based Predicted No‐Effect Concentrations for Copper in Freshwater

Abstract

The copper (Cu) biotic ligand model (BLM) has been used for ecological risk assessment by taking into account the bioavailability of Cu in freshwater. The Cu BLM requires data for many water chemistry variables, such as pH, major cations, and dissolved organic carbon, which can be difficult to obtain from water quality monitoring programs. To develop an optimized predicted no-effect concentration (PNEC) estimation model based on an available monitoring dataset, we proposed an initial model that considers all BLM variables, a second model that requires variables excluding alkalinity, and a third model using electrical conductivity as a surrogate for the major cations and alkalinity. Furthermore, deep neural network (DNN) models have been used to predict the nonlinear relationships between the PNEC (outcome variable) and the required input variables (explanatory variables). The predictive capacity of DNN models was compared with the results of other existing PNEC estimation tools using a look-up table and multiple linear and multivariate polynomial regression methods. Three DNN models, using different input variables, provided better predictions of the Cu PNECs compared with the existing tools for the following four test datasets: Korean, United States, Swedish, and Belgian freshwaters. Consequently, it is expected that Cu BLM–based risk assessment can be applied to various monitoring datasets, and that the most applicable model among the three different types of DNN models could be selected according to data availability for a given monitoring database. Environ Toxicol Chem 2023;42:2271–2283. © 2023 SETAC

Recent Applications of Paired Electrolysis in Organic Synthesis

Recent Applications of Paired Electrolysis in Organic Synthesis


Abstract

Recent years have witnessed a renaissance of organic electrochemistry since the cheap, safe, sustainable electron could be employed as a traceless redox agent to facilitate redox conversions. Additionally, divergent selectivity could be achieved by tuning the potential or current of the electrochemical reaction. Compared to electrooxidation or electroreduction reactions, paired electrolysis represents a more practical and energy-efficient strategy that delivers the products by making use of both anodic and cathodic reactions simultaneously. This mini-review summarized the breakthroughs and recent advances in this fascinating field and mainly is divided into three parts: parallel, sequential, and convergent paired electrolysis.

Assessing the biodegradability of tire tread particles and influencing factors

ABSTRACT

Abrasion of tire tread, caused by friction between vehicle tires and road surfaces, causes release of tire wear particles (TWPs) into various environmental compartments. TWPs contribute to chemical-, microplastic-, and particulate matter pollution. Their fate remains largely unknown, especially regarding the extent and form in which they persist in the environment. This study investigated 1) the biodegradability of tread particles (TPs) in the form of ground tire tread, 2) how accelerated UV-weathering affect their biodegradability, and 3) which TP constituents are likely contributors to TP biodegradability based on their individual biodegradability. A series of closed bottle tests, with aerobic aqueous medium inoculated with activated sludge, were carried out for pristine TPs, UV-weathered TPs, and selected TP constituents; natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), and treated distillate aromatic extracts (TDAE). Biodegradation was monitored by manometric respirometry quantifying biological oxygen consumption over 28 days. Pristine TP biodegradability was found to be 4.5%. UV-weathered TPs showed higher biodegradability of 6.7% and 8.0% with similar and increased inoculum concentration, respectively. The observed TP biodegradation was mainly attributed to biodegradation of NR and TDAE, with individual biodegradability of 35.4% and 8.0%, respectively. IR and BR showed negligible biodegradability. These findings indicate biodegradability of individual constituents is decreased by a factor of 2 to 5 when compounded into TPs. Through scanning electron microscope (SEM) analysis, biodegradation was found to cause surface erosion. Processes of TP biodegradation are expected to change throughout their lifetime as new constituents are incorporated from the road and others degrade and/or leach out. Tire emissions likely persist as particles with an increased fraction of synthetic rubbers and carbon black.

Advances in Continuous Flow Fluorination Reactions

Advances in Continuous Flow Fluorination Reactions

Fluorination reactions are important in constructing organofluorine motifs in pharmaceuticals and agrochemicals, but they pose challenges due to their hazardous nature, high exothermicity, and limited selectivity and scalability. This review explores recent continuous flow techniques that addressed challenges of fluorination reactions, including gas-liquid reactions, packed-bed reactors, in-line purifications, reaction telescoping, large-scale reactions as well as flow photoredox- and electrocatalysis.


Abstract

Fluorination reactions are important in constructing organofluorine motifs, which contribute to favorable biological properties in pharmaceuticals and agrochemicals. However, fluorination reagents and reactions are associated with various problems, such as their hazardous nature, high exothermicity, and poor selectivity and scalability. Continuous flow has emerged as a transformative technology to provide many advantages relative to batch syntheses. This review article summarizes recent continuous flow techniques that address the limitations and challenges of fluorination reactions. Approaches based on different flow techniques are discussed, including gas-liquid reactions, packed-bed reactors, in-line purifications, streamlined multistep synthesis, large-scale reactions well as flow photoredox- and electrocatalysis.

LPMO‐like activity of bioinspired copper complexes: from model substrate to extended polysaccharides

Polysaccharide oxidative depolymerization is highly desirable to achieve recalcitrant biomass valorization. Inspired by recently discovered Lytic Polysaccharide Monooxygenases, mononuclear copper complexes have been prepared and studied in the literature. However, the activities were evaluated on different substrates and under various conditions. In this work we intended to establish a robust and reproducible activity assay, in aqueous solution at a pH close from neutrality and under mild conditions. We have evaluated several complexes on substrates of increasing complexity: the model substrate para-nitrophenyl-β-D-glucopyranoside (p-NPG), cellobiose (glucose dimer), as well as on extended substrates (chitin, cellulose and bagasse from agave). The different assays were compared and proof-of-concept that bioinspired complexes can oxidatively promote polysaccharide depolymerization was obtained. Finally, we measured level of hydroxyl radicals released by the complexes under comparable experimental conditions and mechanistic pathways are discussed.