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Natural dissolved organic matter (DOM) is a heterogeneous mixture of a variety of organic compounds, with a great importance for the environmental fate of metals and their ecotoxicity. However, its complex nature and variable composition make the understanding of its role a challenge. Lanthanum (La) has a strong affinity for DOM and is one of the rare earth elements that is widely used in many electronic and green technologies, and for which the demand may potentially increase for the foreseeable future. The present study examines the links between the optical and chemical properties of organic matter and its influence on the bioavailability and toxicity of La toward the green microalga Chlorella fusca. A total of four DOMs, two natural organic matter samples from Ontario (Luther Marsh and Bannister Lake) and two Suwannee River fulvic and humic acids, were characterized by absorbance and fluorescence spectroscopy as well as by asymmetrical flow field-flow fractionation. These suggest that Luther Marsh and the Suwannee River humic acid have higher molecular weight and are more aromatic, compared to the other two DOMs. The concentrations of free metal iosn La3+ were measured by an ion exchange technique and a partial ultrafiltration method, and related to biological response. Toxicity tests over 96 h at pH = 5.0 were separately conducted with and without 3mgC·L-1 of each DOM. All DOM samples reduced La bioavailability but as opposed to what can be expected based on the Biotic Ligand Model, the presence of DOM exacerbated the toxicity of La and its accumulation in algal cells when only the free La3+ ion concentration was considered. These results indicate that the role of natural organic matter in modulating metal bioavailability remains to be deciphered. [ABSTRACT FROM AUTHOR]

Environmental context: Thiosulfate is present in natural waters, especially those influenced by sulfide oxidation, and it has a marked affinity for metals such as cadmium. Normally the binding of cadmium by thiosulfate would be expected to reduce the metal's bioavailability. However, here we demonstrate that algal uptake of cadmium is enhanced in the presence of thiosulfate, indicating that Cd can enter the alga via a novel route as an intact Cd-thiosulfate complex. Rationale: For a given free metal ion activity in the exposure solution, the Biotic Ligand Model assumes that metal uptake will be independent of the various ligands present in solution that are buffering [M z +]. In this context, we have evaluated cadmium bioavailability in the absence or presence of thiosulfate, using Chlamydomonas reinhardtii as the test alga. Methodology: Short-term exposures (≤41 min) were run with a fixed concentration of the free Cd2+ ion (3.0 ± 0.1 nM), buffered with either nitrilotriacetate or thiosulfate, to determine Cd uptake. Subsequent long-term exposures (72 h) over a range of free Cd2+ concentrations were used to determine the effects of Cd on algal growth. Results: Contrary to Biotic Ligand Model predictions, Cd uptake was enhanced when Cd2+ was buffered with thiosulfate. Removal of sulfate from this exposure medium increased Cd uptake; conversely, if [SO42−] was increased, Cd uptake decreased. In the absence of thiosulfate, Cd uptake was unaffected by changes in [SO42−]. In the long-term exposures, the cellular Cd quota needed to reduce algal growth by 50% was significantly higher in the presence of thiosulfate than in its absence. Discussion: In the presence of thiosulfate, Cd can enter the algal cell not only by cation transport but also by transport of the intact Cd-thiosulfate complex via the anion transporter responsible for sulfate uptake. We speculate that some of the Cd taken up by anion transport remains in complexed form and is less bioavailable than the Cd that enters the cell via cation transport. Environmental context. Thiosulfate is present in natural waters, especially those influenced by sulfide oxidation, and it has a marked affinity for metals such as cadmium. Normally the binding of cadmium by thiosulfate would be expected to reduce the metal's bioavailability. However, here we demonstrate that algal uptake of cadmium is enhanced in the presence of thiosulfate, indicating that Cd can enter the alga via a novel route as an intact Cd-thiosulfate complex. [ABSTRACT FROM AUTHOR]

Environmental context: The growth in demand for platinum has led to an increase in the presence of this metal in the environment but little is known about its toxicity to aquatic organisms. The presence of organic matter should contribute to decreasing metal bioavailability but the opposite was found for platinum. How ubiquitous natural organic matter can alter the accumulation and effects of platinum group elements remains to be fully elucidated. Rationale: There is a growing interest for platinum in ecotoxicology, mainly because of its use in automobile exhaust catalysts. When it reaches aquatic ecosystems, platinum can interact with ligands such as natural organic matter. According to the Biotic Ligand Model, the formation of such complexes should reduce metal bioavailability. As a consequence, toxicity should decrease in the presence of organic matter. Methodology: This study focused on the uptake of platinum by two microalgae species (Chlorella fusca and Chlamydomonas reinhardtii) and its subsequent inhibitory effects on growth (96 h). Cells were exposed to platinum (5–300 µg L−1) at three concentrations (0, 10 and 20 mg C L−1) of standard Suwannee River humic acid (SRHA). Platinum bound to humic acid was determined experimentally using partial ultrafiltration to relate metal uptake and toxicity to speciation. Results: Unexpectedly, results show that platinum toxicity, expressed as ultrafiltrable Pt (not bound to humic acid) and total Pt concentrations, is enhanced in the presence of humic acid for both algae. For C. fusca , the half maximal effective concentration (EC50) values decreased from 93 to 37 and 35 µg L−1 of ultrafiltrable Pt in the presence of 10 and 20 mg C L−1 SRHA and from 89 to 36 and 0.31 µg L−1 for C. reinhardtii. Discussion: In contradiction with the Biotic Ligand Model, the results show that the presence of SRHA can significantly and importantly increase platinum uptake and toxicity as determined in two unicellular green algae, C. reinhardtii and C. fusca. The present work raises the issue of the impact of platinum on microalgae under realistic environmental conditions (ubiquitous presence of organic matter), primary producers being of great ecological importance. Environmental context. The growth in demand for platinum has led to an increase in the presence of this metal in the environment but little is known about its toxicity to aquatic organisms. The presence of organic matter should contribute to decreasing metal bioavailability but the opposite was found for platinum. How ubiquitous natural organic matter can alter the accumulation and effects of platinum group elements remains to be fully elucidated. [ABSTRACT FROM AUTHOR]

The environmental risk assessment of rare earth elements (REEs) requires data on their potential toxicity. In the present study, the toxicity of lanthanum (La) and cerium (Ce) was studied in relation to metal speciation in solution. For both La and Ce, the use of organic ligands demonstrated that the calculated free ion concentration was a good indicator of toxicity. Whether in the absence or presence of organic ligands, when based on free ion concentrations, the obtained half‐maximal effective concentrations were similar. When all generated data were pooled, Ce and La showed identical toxicity thresholds after 120 h of exposure with free ion concentration–based median effective concentration values (95% confidence intervals) of 0.48 (0.38–0.60) µM and 0.47 (0.36–0.61) µM for La3+ and Ce3+, respectively. The inhibition of algal growth was also correlated with the intracellular lanthanide concentrations, regardless of the ligand used. Finally, increasing the ambient calcium concentration protected the test algae by reducing the amount of lanthanide internalized into the cells. These results suggest that, at constant pH (5.5), REE accumulation and toxicity are linked to the free ion concentration and ambient calcium concentration, as predicted by the biotic ligand model. Environ Toxicol Chem 2020;39:996–1005. © 2020 SETAC [ABSTRACT FROM AUTHOR]

Abstract Aluminum (Al) is widespread in the environment including the ocean. The effects of Al on marine organisms have attracted more and more attention in recent years. However, the mechanisms of uptake of Al by marine organisms and the subcellular distribution of Al once assimilated are unknown. Here we report the uptake and subcellular distribution of Al in a marine diatom Thalassiosira weissflogii. Short-term (< 120 min) uptake experiments showed that the Al uptake rate by the diatom was 0.033 ± 0.013 fmol-1 cell-1 min-1 (internalization flux normalized to the exposure Al concentration of 2 µM = 0.034 ± 0.013 nmol m−2 min−1 nM−1). Subcellular fractionation experiments showed that the internalized Al was partitioned to subcellular components in the following order: granules (69 ± 5%) > debris (17 ± 4%) > organelles (12 ± 2%) > heat-stable peptides (HSP) (~2%) > heat-denaturable proteins (HDP) (< 1%), indicating that the majority of intracellular Al was detoxified and stored in inorganic forms. The subcellular distribution of Al in the diatom is different from that of Al in freshwater green algae, in which most of the internalized Al is partitioned to organelles. We also evaluated an artificial seawater-based EDTA rinse solution to remove Al adsorbed on the diatom cell surface. Overall, our study provides new information to understand the mechanisms of uptake of Al by marine diatoms, and the mechanisms responsible for the biological effects (both toxic and beneficial) of Al on the growth of marine phytoplankton, especially diatoms. Graphic Abstract fx1 Highlights • Little is known about the uptake of Al by marine algae and its intracellular fate. • Aluminum can cross the plasmalemma of a marine diatom and accumulate within the alga. • Internalized Al is bound largely as insoluble granules (~ 70%) followed by debris (17%) and organelles (12%). • A seawater-based EDTA rinse solution was tested for removal of Al adsorbed on the algal cell surface. [ABSTRACT FROM AUTHOR]

The effects of pH on metal uptake and toxicity in aquatic organisms are currently poorly understood and remain an evolving topic in studies about the biotic ligand model (BLM). In the present study, the authors investigated how pH may influence long-term (4 d) uranium (U) accumulation and chronic toxicity in batch cultures of the freshwater green alga Chlamydomonas reinhardtii. The toxicity expressed as a function of the free uranyl ion was much greater at pH 7 (effective concentration, 50% [EC50] = 1.8 × 10−9 M UO22+) than at pH 5 (EC50 = 1.2 × 10−7 M UO22+). The net accumulation rate of U in algal cells was much higher at pH 7 than at pH 5 for the same free [UO22+], but the cells exposed at pH 5 were also more sensitive to intracellular U than the cells at pH 7 with EC50s of 4.0 × 10−15 and 7.1 × 10−13 mol of internalized U cell−1, respectively. The higher cellular sensitivity to U at pH 5 than at pH 7 could be explained partly by the increase in cytosolic U binding to algal soluble proteins or enzymes at pH 5 as observed by subcellular fractionation. To predict U accumulation and toxicity in algae accurately, the important modulating effects of pH on U accumulation and U cellular sensitivity should be considered in the BLM. Environ Toxicol Chem 2014;33:1372-1379. © 2014 SETAC [ABSTRACT FROM AUTHOR]

Background We examined the uptake and sorption of aluminium (Al) and fluoride (F) by green algae under conditions similar to those found in the effluents of the aluminium industry. We took into account the speciation of Al in the medium since Al can form stable complexes with F and these complexes may play a role in the uptake and sorption of Al. We compared the capacity of four species of green algae (i.e. Chlamydomonas reinhardtii, Pseudokirchneriella subcapitata, Chlorella vulgaris, and Scenedesmus obliquus) to accumulate and adsorb Al and F. The selected algae were exposed during 4 days, covering all growth phases of algae, to a synthetic medium containing Al and F at pH 7.0. During this period, dissolved Al as well as cellular growth were followed closely. At the end of the exposure period, the solutions were filtered in order to harvest the algal cells. The cells were then rinsed with enough ethylene diaminetetraacetic acid to remove loosely bound ions from the algal surface, determined from the filtrates. Finally, the filters were digested in order to quantify cellular uptake. Results Little difference in Al removal was observed between species. Aluminium sorption (15%) and uptake (26%) were highest in P. subcapitata , followed by C. reinhardtii (7% and 17% respectively), S. obliquus (13% and 5%), and C. vulgaris (7% and 2%). However, none of these species showed significant uptake or sorption of F. We also studied the influence of pH on the uptake and sorption of Al and F by P. subcapitata. We measured a combined uptake and sorption of Al of 50% at pH 7.5, of 41% at pH 7.0, and of 4% at pH 5.5. Thus, accumulation was reduced with acidification of the medium as expected by the increased competition with protons and possibly by a reduced bioavailability of the Al-F complexes which dominated the solution at low pH. Conclusion Out of the four tested species, P. subcapitata showed the highest sorption of aluminium and fluoride under our test conditions. These results provide key information on the development of an environmental biotechnology which can be applied to industrial effluents. [ABSTRACT FROM AUTHOR]

Within the biotic ligand model (BLM) construct, major cations are considered to be simple competitors for metal binding to uptake sites and may offer some protection against metal-induced toxicity, but the influence of essential trace elements and cell preconditioning to different micronutrient concentrations on metal uptake and toxicity is considered negligible. To test these underlying assumptions, we monitored Cd uptake and toxicity in a green alga ( Chlamydomonas reinhardtii) after long-term exposures (60 h) to a range of environmentally realistic free Zn2+, Co2+, Fe3+, Mn2+, Ca2+, and Cu2+ concentrations buffered with nitrilotriacetic acid. A 200-fold increase in free [Mn2+] as well as a 100-fold increase in free [Fe3+] did not affect Cd uptake or toxicity, whereas a 50-fold increase in free [Ca2+] effectively offered some protection, as predicted by the BLM. However, a 10-fold increase in free [Cu2+] significantly enhanced Cd toxicity by a factor of approximately 2, whereas a 100-fold increase in free [Zn2+] and [Co2+] from 10−11 to 10−9 M significantly decreased Cd uptake and toxicity by more than twofold. These effects did not change with prior algal acclimation to different essential micronutrient concentrations. Low essential trace metal concentrations may strongly affect the uptake and toxicity of Cd in freshwater algae and should be taken into consideration in future developments of the BLM. Environ. Toxicol. Chem. 2012; 31: 1445-1452. © 2012 SETAC [ABSTRACT FROM AUTHOR]

Cadmium forms neutral, lipophilic CdL20 complexes with diethyldithiocarbamate (L = DDC) and with ethylxanthate (L = XANT). In a synthetic solution and in the absence of natural dissolved organic matter (DOM), for a given total Cd concentration, uptake of these complexes by unicellular algae is much faster than the uptake of the free Cd2+ cation. The objective of the present study was to determine how this enhanced uptake of the lipophilic CdL20 complexes was affected by the presence of natural DOM (Suwannee River humic acid, SRHA). Experiments were performed with Cd(DDC)20 and Cd(XANT)20 at two pH values (7.0 and 5.5) and with the three chlorophytes [ Chlamydomonas reinhardtii P. A. Dang., Pseudokirchneriella subcapitata (Korshikov) Hindák, Chlorella fusca var. vacuolata Shihira et R. W. Krauss]. Short-term uptake (30-40 min) of the CdL20 complexes was followed in the absence and presence of SRHA (6.5 mg C · L−1). Acidification from pH 7.0 to 5.5 decreased CdL20 uptake by the three algae, in the presence or absence of humic acid (HA). The dominant effect of the HA was to decrease Cd uptake, due to its interaction with the CdL20 complexes in solution. However, if uptake of the free CdL20 complexes was compared in the presence and absence of HA, in four of eight cases initial uptake rate constants ( ki) were significantly higher ( P < 0.05) in the presence of the HA, suggesting the operation of an interfacial effect of the HA at the algal cell membrane, favoring uptake of CdL20. Overall, the experimental results suggest that neutral metal complexes will be less bioavailable in natural waters than they are in synthetic laboratory media in the absence of natural DOM. [ABSTRACT FROM AUTHOR]

The influence of time, ambient concentration, and medium composition on selenite (Se(IV)) uptake by the unicellular green alga Chlamydomonas reinhardtii has been investigated. The aims of the performed experiments were to describe the kinetics of accumulation, to characterize transport capacities, to identify key nutrients influencing absorption, and to establish links between speciation and bioavailability. Our results suggested that the adsorbed fraction was negligible compared to the absorbed one. Over the short time scale considered, the absorption was linear with time, with an estimated conductance of approximately 0.2 nmol/ m2/h/nM. Uptake was proportional to ambient levels in a broad range of intermediate concentrations (from nM to µM). However, conductances were higher at low concentrations (

Abstract: Short-term silver toxicity was determined for two freshwater algae, Pseudokirchneriella subcapitata and Chlamydomonas reinhardtii, in the presence and absence of chloride. Silver speciation in the exposure media was controlled and algal growth was measured over 6h. For P. subcapitata, an alga with low Ag uptake fluxes, silver toxicity could be predicted on the basis of the free Ag+ concentration, in the presence or absence of significant complexation by chloride ions, as predicted by the biotic ligand model (BLM). For C. reinhardtii, an alga with high Ag uptake fluxes, silver toxicity was better predicted by the concentration of all labile dissolved Ag species than by free silver, a result that is consistent with diffusion through the unstirred layer surrounding the cell surface being the rate-limiting step in silver uptake. For both species, growth inhibition could be predicted on the basis of the Ag intracellular quota in the presence or absence of chloride, indicating that silver toxicity is a direct result of intracellular accumulation rather than cell surface interactions. [Copyright &y& Elsevier]

Silver bioavailability in the presence of chloride was estimated from short-term (≤60 min) uptake experiments with two green algae, Pseudokirchneriella subcapitata and Chlorella pyrenoidosa. In the first experiment, silver uptake was monitored under two concentration regimes in which total dissolved silver ([Ag]tot) and [C1] were manipulated to maintain [Ag+] at a constant value (10 nM). Comparable uptake rates were measured for both treatments despite the dramatic changes in [C1] and [Ag]tot. In the second experiment, ambient [Ag]tot was held constant (10 or 115 nM), but [C1] was varied (0.005-50 mM) to explore the whole range of silver chloro-complexes. Intracellular silver varied markedly along the [C1] gradient and exhibited a clear, positive correlation with ambient [Ag+] for both algae. We conclude that the biotic ligand model reliably describes silver bioavailability in the presence of chloride for the two test algae and that its applicability depends on the relative magnitudes of silver fluxes through the unstirred diffusion layer and across the cell membrane, with the latter being affected by the presence or absence of a Cu(I) transporter. In the presence of chloride, no evidence was found for the internalization of silver via anion transport or passive diffusion of the neutral mono-chloro-complex, AgCl0. [ABSTRACT FROM AUTHOR]

Short-term (<1 h) silver uptake by the green alga Chlamydomonas reinhardtii was measured in the laboratory in defined inorganic media over a range of silver and chloride concentrations. For a low, fixed, free Ag+ concentration (e.g., 8 nM), silver uptake increases markedly (up to ∼43) as a function of the chloride concentration (5 μM→4 mM C1-); the free-ion model would have predicted a constant silver uptake rate. No evidence could be found for the passive diffusion of the neutral AgC1-0 complex or for the facilitated uptake of the anionic AgCl-2 complex. The enhanced uptake observed in the presence of chloride is related to the very high silver uptake rates demonstrated by the test alga, which lead to diffusion limitation in the boundary layer surrounding the algal cell. In such a situation, metal accumulation is proportional to the total metal concentration (i.e., to the concentration gradient between the bulk solution and the algal surface). At higher silver concentrations (e.g.,≥10-7M), diffusion in the phycosphere is no longer rate limiting, the chloride stimulation disappears, and silver uptake is sensitive to the free-ion concentration. However, such a high concentration of silver is not likely to be encountered in the environment, even in wastewater effluents. [ABSTRACT FROM AUTHOR]

This study refines the Biotic Ligand Model (BLM) approach by integrating the modulating effects of various essential elements on cadmium (Cd) uptake kinetics in the freshwater alga Chlamydomonas reinhardtii. The algae were first acclimated to a low (LM) or high trace metal (HM) medium as well as to low or high free Cd2+ and Co2+ concentrations. The short-term Cd transport capacity and affinity were then quantified in exposure media in which essential trace metals and calcium concentrations were manipulated. The results show that after acclimation to the LM medium, exposure to high free Ca2+ decreases the capacity of the Cd transport system. Also, acclimation to high (10-9 M free Co2+) or low (10-11 M free Co2+) did not significantly affect Cd uptake rates. When all essential trace metals were simultaneously increased in the acclimation (and exposure) medium, the capacity of the transport system decreased by ∼60%, a decrease close to that due to high [Zn2+] alone, suggesting that Zn is the main trace metal modulator of the Cd transporter capacity. Changes in Cd toxicity (growth inhibition) in the presence of different essential trace metal concentrations were strongly related to the steady-state concentration of intracellular cadmium, regardless of the cell's nutritional state. Our BLM incorporating the physiological effects of Ca2+ and other trace metals predicts steady-state Cd accumulation in the presence of varying concentrations of essential elements at 7 nM free Cd2+, but predictions over a wide range of free [Cd2+] proved to be more difficult. [ABSTRACT FROM AUTHOR]

Abstract: The effect of core–shell copper oxide nanoparticles with sizes smaller than 100nm on cellular systems is still not well understood. Documenting these effects is pressing since core–shell copper oxide nanoparticles are currently components of pigments used frequently as antifouling paint protecting boats from crustacean, weed and slime fouling. However, the use of such paints may induce strong deteriorative effects on different aquatic trophic levels that are not the intended targets. Here, the toxic effect of core–shell copper oxide nanoparticles on the green alga, Chlamydomonas reinhardtii was investigated with regards to the change of algal cellular population structure, primary photochemistry of photosystem II and reactive oxygen species formation. Algal cultures were exposed to 0.004, 0.01 and 0.02g/l of core–shell copper oxide nanoparticles for 6h and a change in algal population structure was observed, while the formation of reactive oxygen species was determined using the 2′,7′-dichlorodihydrofluorescein diacetate marker measured by flow cytometry. For the study of the photosystem II primary photochemistry we investigated the change in chlorophyll a rapid rise of fluorescence. We found that core–shell copper oxide nanoparticles induced cellular aggregation processes and had a deteriorative effect on chlorophyll by inducing the photoinhibition of photosystem II. The inhibition of photosynthetic electron transport induced a strong energy dissipation process via non-photochemical pathways. The deterioration of photosynthesis was interpreted as being caused by the formation of reactive oxygen species induced by core–shell copper oxide nanoparticles. However, no formation of reactive oxygen species was observed when C. reinhardtii was exposed to the core without the shell or to the shell only. [Copyright &y& Elsevier]