Metal-organic frameworks (MOFs) are an emerging class of materials which have garnered increasing attention for their utility as adsorbents and photocatalysts in water treatment. Nevertheless, the environmental risks of MOFs, especially their underlying impacts on aquatic organisms, are not fully explored. Herein, the toxicity of multiple representative MOFs was systematically assessed using a freshwater green alga (Chlamydomonas reinhardtii) model. Six typical MOFs with different metal nodes or organic linkers, including four transition metal incorporated aluminum-based porphyrin MOFs [pristine Al-PMOF, Al-PMOF (Cu), Al-PMOF (Ni), and Al-PMOF (Co)], one amine-functionalized MOF NH₂-MIL-125 (Ti), and one bimetallic Hofmann MOF (NiCo-PYZ), were successfully synthesized and characterized. All the tested MOFs significantly reduced the chlorophyll content and inhibited the algal growth, with the most toxic materials being NiCo-PYZ and Al-PMOF (Cu). Distinct toxic mechanisms were observed for the tested MOFs. Metal ion release was the primary cause for algal toxicity induced by NiCo-PYZ. The algal toxicity induced by porphyrin MOFs could be explained by the combined effects of metal ion release and nutrient adsorption, agglomeration and physical interactions, and reactive oxygen species generation. NH₂-MIL-125 (Ti) showed higher stability and more biocompatibility than the other tested MOFs. MOFs concentrations with no harmful effects to algae can be taken as the threshold values for safe use and discharge of MOFs. The ecotoxicological risks of MOFs should be considered as the applied concentrations of MOFs at mg/mL levels in environmental remediation were much higher than the no harmful effect thresholds.

The wide range of industrial applications of chromium (Cr) has led to an increasing risk of water contamination by Cr(Ⅵ). However, efficient methods to remove or decrease the toxicity of Cr(Ⅵ) in situ are lacking. The main aim of this study was to investigate the mechanisms by which selenite alleviates chromium(Ⅵ)-induced toxicity in Chlamydomonas reinhardtii. Our results showed that K₂Cr₂O₇ had toxic effects on both the structure and physiology of C. reinhardtii in a dose-dependent manner. Adding selenite significantly alleviated chromium accumulation and toxicity in cells. RNA-seq data showed that the expression level of selenoproteins such as SELENOH was significantly increased. Both SELENOH-amiRNA knockdown mutants and selenoh insertional mutant produced more reactive oxygen species (ROS) and grew slower than the wild type, suggesting that SELENOH can reduce chromium toxicity by decreasing the levels of ROS produced by Cr(Ⅵ). We also demonstrated that selenite can reduce the absorption of Cr(Ⅵ) by cells but does not affect the process of Cr(Ⅵ) adsorption and efflux. This information on the molecular mechanism by which selenite alleviates Cr(Ⅵ) toxicity can be used to increase the bioremediation capacity of algae and reduce the human health risks associated with Cr(Ⅵ) toxicity.

In the present study, we evaluate our previously developed non-destructive soil algal toxicity method using species from a different class of algae; Class Trebouxiophyceae (Chlorella vulgaris and Chlorella sorokiniana), and directly measure the photosynthetic activity of these species adsorbed onto the soil as a new toxicity endpoint. This study shows that non-destructive soil algal toxicity method is applicable to non-specific test species, including those of Class Trebouxiophyceae as well as Class Chlorophyceae (Chlorococcum infusionum and Chlamydomonas reinhardtii). Furthermore, by performing photosynthesis image analysis, we verify that it is possible to measure the photosynthetic activity of soil algae Chlorella vulgaris adsorbed onto soils without the need to extract algal cells from the soil. We propose that the non-destructive soil algal toxicity method represents a novel technique for 1) evaluating pollutants in soil using non-specific algae and 2) conveniently and rapidly assessing the photosynthetic activity of soil algae Chlorella vulgaris adsorbed onto soil as a new toxicity endpoint.

Triclosan (TCS) is a broad-spectrum antimicrobial agent that is found extensively in natural aquatic environments. Enzyme-catalyzed oxidative coupling reactions (ECOCRs) can be used to remove TCS in aqueous solution, but there is limited information available to indicate how metal cations (MCs) and natural organic matter (NOM) influence the environmental fate of TCS during laccase-mediated ECOCRs. In this study, we demonstrated that the naturally occurring laccase from Pleurotus ostreatus was effective in removing TCS during ECOCRs, and the oligomerization of TCS was identified as the dominant reaction pathway by high-resolution mass spectrometry (HRMS). The growth inhibition studies of green algae (Chlamydomonas reinhardtii and Scenedesmus obliquus) proved that laccase-mediated ECOCRs could effectively reduce the toxicity of TCS. The presence of dissolved MCs (Mn²⁺, Al³⁺, Ca²⁺, Cu²⁺, and Fe²⁺ ions) influenced the removal and transformation of TCS via different mechanisms. Additionally, the transformation of TCS in systems with NOM derived from humic acid (HA) was hindered, and the apparent pseudo first-order kinetics rate constants (k) for TCS decreased as the HA concentration increased, which likely corresponded to the combined effect of both noncovalent (sorption) and covalent binding between TCS and humic molecules. Our results provide a novel insight into the fate and transformation of TCS by laccase-mediated ECOCRs in natural aquatic environments in the presence of MCs and NOM.

The present study examines the effect of carboxyl-CdSe/ZnS quantum dots (QDs) on Cu and Pb availability to microalgae with different cell wall characteristics: Chlorella kesslerii possessing a cellulosic cell wall and two strains of Chlamydomonas reinhardtii, a wall-less and a walled strain containing glycoproteins as the main cell wall component. Results demonstrated that QDs decreased Pb and Cu intracellular contents ({Cu}ᵢₙₜ and {Pb}ᵢₙₜ) in walled strains by a factor of 2.5 and 2, respectively, as expected by the decrease of about 70% and 40% in the dissolved Cu and Pb concentrations. QDs increased {Cu}ᵢₙₜ and {Pb}ᵢₙₜ in wall-less strain by a factor of 4 and 3.5. These observations were consistent with the observed association of QDs to the wall-less C. reinhardtii, and lack of association to walled algal strains. Suwannee River humic acid did not influence metal association to QDs, but decreased {Cu}ᵢₙₜ and {Pb}ᵢₙₜ in all microalgae.

In situ measurements provide data that are the highly representative of the natural environment. In this paper, laboratory-determined biomarkers of Cd stress that were previously identified for the green alga Chlamydomonas reinhardtii, were tested in two French rivers: a contaminated site on the Riou Mort River and an “uncontaminated” reference site on the Lot River. Transcript abundance levels were determined by real time qPCR for biomarkers thought to be Cd sensitive. Transcript levels were significantly higher (>5 fold) for organisms exposed to the contaminated site as compared to those exposed at the uncontaminated site. Biomarker mRNA levels were best correlated to free Cd (Cd²⁺) rather than intracellular Cd, suggesting that they may be useful indicators of in situ stress. The paper shows that biomarker expression levels increased with time, were sensitive to metal levels and metal speciation and were higher in the “contaminated” as opposed to the “reference” site.

In order to better understand the environmental risks of the rare earth elements (REEs), it is necessary to determine their fate and biological effects under environmentally relevant conditions (e.g. at low concentrations, REE mixtures). Here, the unicellular freshwater microalga, Chlamydomonas reinhardtii, was exposed for 2 h to one of three soluble REEs (Ce, Tm, Y) salts at 0.5 μM or to an equimolar mixture of these REEs. RNA sequencing revealed common biological effects among the REEs. Known functions of the differentially expressed genes support effects of REEs on protein processing in the endoplasmic reticulum, phosphate transport and the homeostasis of Fe and Ca. The only stress response detected was related to protein misfolding in the endoplasmic reticulum. When the REEs were applied as a mixture, antagonistic effects were overwhelmingly observed with transcriptomic results suggesting that the REEs were initially competing with each other for bio-uptake. Metal biouptake results were consistent with this interpretation. These results suggest that the approach of government agencies to regulate the REEs using biological effects data from single metal exposures may be a largely conservative approach.

Though the main toxic mechanisms of graphene oxide (GO) to algae have been accepted as the shading effect, oxidative stress and mechanical damage, the effect of algal characteristics on these three mechanisms of GO toxicity have seldom been taken into consideration. In this study, we investigated GO toxicity to green algae (Chlorella vulgaris, Scenedesmus obliquus, Chlamydomonas reinhardtii), cyanobacteria (Microcystis aeruginosa) and diatoms (Cyclotella sp.). The aim was to assess how the physiological characteristics of algae affect the toxicity of GO. Results showed that 10 mg/L of GO significantly inhibited the growth of all tested algal types, while S. obliquus and C. reinhardtii were found to be the most susceptible and tolerant species, respectively. Then, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to observe the physiological characteristics of the assessed algae. The presence of locomotive organelles, along with smaller and more spherical cells, was more likely to alleviate the shading effect. Variations in cell wall composition led to different extents of mechanical damage as shown by Cyclotella sp. silica frustules and S. obliquus autosporine division being prone to damage. Meanwhile, growth inhibition and cell division were significantly correlated with the oxidative stress and membrane permeability, suggesting the latter two indicators can effectively signal GO toxicity to algae. The findings of this study provide novel insights into the toxicity of graphene materials in aquatic environments.

Microalgae are widely used as representative primary producers in ecotoxicology, while macrophytes are much less studied. Here we compared the bioavailability and cellular toxicity pathways of 2 h-exposure to 10−6 mol L−1 Cu in the macrophyte Elodea nuttallii and the green microalga Chlamydomonas reinhardtii.Uptake rate was similar but faster in the algae than in the macrophyte, while RNA-Sequencing revealed a similar number of regulated genes. Early-regulated genes were congruent with expected adverse outcome pathways for Cu with Gene Ontology terms including gene regulation, energy metabolism, transport, cell processes, stress, antioxidant metabolism and development. However, the gene regulation level was higher in E. nuttallii than in C. reinhardtii and several categories were more represented in the macrophyte than in the microalga. Moreover, several categories including oxidative pentose phosphate pathway (OPP), nitrate metabolism and metal handling were only found for E. nuttallii, whereas categories such as cell motility, polyamine metabolism, mitochondrial electron transport and tricarboxylic acid cycle (TCA) were unique to C. reinhardtii. These differences were attributed to morphological and metabolic differences and highlighted dissimilarities between a sessile and a mobile species. Our results highlight the efficiency of transcriptomics to assess early molecular responses in biota, and the importance of studying more aquatic plants for a better understanding on the impact and fate of environmental contaminants.

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.