Phytotoxicity of single and mixed rare earth element (La, Nd and Sm) exposures on Lactuca sativa seed germination and growth.

The mode of action, bioaccumulation potential and toxicity of Rare Earth Elements (REE), with several applications in the technology, medical and agricultural fields, are still understudied. The nitrates acute effects on single exposures, binary and ternary mixtures of lanthanum (La), neodymium (Nd) and samarium (Sm) on Lactuca sativa lettuce seed germination and wet biomass in an artificial soil (AS) and an Ultisol were assessed. Germination (EC50), wet biomass (IC50) and germination inhibition (% GI) were evaluated. EC50 values show La was the most toxic in Ultisol, Sm in AS, and Nd appears with intermediate values on both substrates. The IC50, both single and mixed, decreased from 3- to 181-fold with increasing test concentrations in relation to the control in AS, while increases in Ultisol were observed, followed by decreases at higher doses which may be associated with the low-dose stimulation effect (hormesis). Our findings may be used to subsidize REE risk assessment studies and reinforce the hormesis effect to prevent the use of high application of REE fertilizers, avoiding the accumulation of REE in agricultural soils.

Acute toxicity of single and combined rare earth element exposures towards Daphnia similis.

The increasing use of Rare Earth Elements (REE) in emerging technologies, medicine and agriculture has led to chronic aquatic compartment contamination. In this context, this aimed to evaluate the acute toxic effects of lanthanum (La), neodymium (Nd) and samarium (Sm), as both single and binary and ternary mixtures on the survival of the microcrustacean Daphnia similis. A metal solution medium with (MS) and without EDTA and cyanocobalamin (MSq) as chelators was employed as the assay dilution water to assess REE bioavailability effects. In the single exposure experiments, toxicity in the MS medium decreased following the order La > Sm > Nd, while the opposite was noted for the MSq medium, which was also more toxic than the MS medium. The highest MS toxicity was observed for the binary Nd + La (1:1) mixture (EC50 48 h of 11.57 ± 1.22 mg.L-1) and the lowest, in the ternary Sm + La + Nd (2:2:1) mixture (EC50 48 h 41.48 ± 1.40 mg.L-1). The highest toxicity in the MSq medium was observed in the single assays and in the binary Sm + Nd (1:1) mixture (EC50 48 h 10.60 ± 1.57 mg.L-1), and the lowest, in the ternary Sm + La + Nd (1:2:2) mixture (EC50 48 h 36.76 ± 1.54 mg.L-1). Concerning the MS medium, 75 % of interactions were additive, 19 % antagonistic, and 6 % synergistic. In the MSq medium, 56 % of interactions were synergistic and 44 % additive. The higher toxicity observed in the MSq medium indicates that the absence of chelators can increase the concentrations of more toxic free ions, suggesting that the MS medium should be avoided in REE assays. Additive interactions were observed in greater or equivalent amounts in both media and were independent of elemental mixture ratios. These findings improve the understanding of environmental REE effects, contributing to the establishment of future guidelines and ecological risk calculations.

Effects of rare earth elements (REE) on terrestrial organisms: current status and future directions.

Rare Earth Elements (REE) are becoming increasingly important economically and highly exploited, thus contributing to REE increases in ecosystems. The ecotoxicological effects of REE on the terrestrial environment are, however, not fully understood and information on the biological effects of REE is urgently required for environmental risk assessments. In this review, studies and gaps in the existing scientific literature regarding the toxicological effects of REE on terrestrial organisms are presented. A total of 41 articles from the Web of Science database are discussed. La and Ce are the most studied elements, while little information is found concerning heavy REE. Most studies have been performed on plant species and few investigations are available for animals. Plant effects such as reduced mitotic index, germination and photosynthesis and antioxidant system enzyme alterations have been reported. Invertebrate effects include mortality, reproduction alterations and reduced locomotion. Based on the limited number of articles on terrestrial environment REE effects, this review highlights the need for more detailed studies in order to elucidate the effects associated with the REE hormesis and perform complete risk assessments with the establishment of safe REE usage limits.

Ecotoxicological assessment of bauxite residue (red mud) overflow treated by dissolved air flotation (DAF).

In this study, the effluent from the Bayer process of transforming bauxite into alumina, followed by dissolved air flotation (DAF) treatment, was evaluated to identify the best experimental conditions that generate less toxic or nontoxic effluent for discharge. Two freshwater organisms, the Chlorophyceae microalga Raphidocelis subcapitata (96-h algal growth inhibition test), and the microcrustacean Daphnia similis (48-h acute immobility test), were used to analyze the efficiency of effluent treatment by detecting and comparing the toxicity of the treated effluent. Experimental factorial planning used different concentrations of the coagulant ferric chloride and the flocculant Nalco® N-99-005B, and different recycle ratios. The highest recycle ratio (30%) and highest flocculant concentration (150 mg/L) had the best solids removal efficiency, above 90%. Probably the higher concentration of flocculant led to the formation of a more stable froth, promoting an increase in the hydrophobic characteristics of the flocs. Two operating conditions were satisfactory according to acute and chronic bioassays, with removal efficiencies of total suspended solids and turbidity higher than 98%, for both variables. Producers, R. subcapitata microalga, were more sensitive than the primary consumers, D. similis microcrustaceans, indicating the importance of performing tests with different bioindicators.

Disposal of dredged sediments in tropical soils: ecotoxicological effects on earthworms.

The upper limit concentrations of metals established by international legislations for dredged sediment disposal and soil quality do not take into consideration the properties of tropical soils (generally submitted to more intense weathering processes) on metal availability and ecotoxicity. Aiming to perform an evaluation on the suitability of these threshold values in tropical regions, the ecotoxicity of metal-contaminated dredged sediment from the Guanabara Bay (Rio de Janeiro, Brazil) was investigated. Acute and avoidance tests with Eisenia andrei were performed with mixtures of dredged sediment with a ferralsol (0.00, 6.66, 13.12, 19.98, and 33.30 %) and a chernosol (0.00, 6.58, 13.16, 19.74, and 32.90 %). Mercury, lead, nickel, chromium, copper, and zinc concentrations were measured in test mixtures and in tissues of surviving earthworms from the acute tests. While ferralsol test mixtures provoked significant earthworm avoidance response at concentrations ≥13.31 %, the chernosol mixtures showed significant avoidance behavior only at the 19.74 % concentration. The acute tests showed higher toxicity in ferralsol mixtures (LC50 = 9.9 %) compared to chernosol mixtures (LC50 = 16.5 %), and biomass increased at the lowest sediment doses in treatments of both test soils. Most probably, the expansive clay minerals present in chernosol contributed to reduce metal availability in chernosol mixtures, and consequently, the ecotoxicity of these treatments. The bioconcentration factors (BCF) for zinc and copper were lower with increasing concentrations of the dredged sediment, indicating the existence of internal regulating processes. Although the BCF for mercury also decreased with the increasing test concentrations, the known no biological function of this metal in the earthworms metabolism lead to suppose that Hg measured was not present in bioaccumulable forms. BCFs estimated for the other metals were generally higher in the highest dredged sediment doses.

Chemical and ecotoxicological indicators for evaluating the treatment of coal mining wastes.

This paper consists of the evaluation in regards to the ecotoxicological effectiveness of a treatment applied to a coal mining waste. The treatment consisted of separating the particles based on gravimetric concentration in spirals, generating three fractions: heavy, intermediate, and light, with high, moderate, and low pyrite content, respectively. The intermediate fraction represents the larger disposal volume of the waste on soils. To evaluate the effectiveness of the treatment, metal determination and bioassays Eisenia andrei, Folsomia candida, Lactuca sativa, Daphnia similis, and Raphidocelis subcapitata were applied to the intermediary fraction. To evaluate the toxicity to aquatic organisms, elutriates were generated from the unprocessed waste and the intermediate fraction. The intermediate fraction showed a decrease of metal concentrations compared to the untreated waste. Metal concentrations in the intermediate fraction were below the Brazilian thresholds for soil quality. Avoidance bioassay with E. andrei and germination tests of L. sativa showed no significant effects. The bioassay with F. candida indicated a significant reduction in reproduction at the highest doses used (24% and 50%). Bioassays with D. similis and R. subcapitata revealed a reduction in toxicity of the intermediate fraction compared to the untreated waste. However, the toxicity levels of the intermediate fraction to aquatic organisms still require attention, especially in regards to pH that played a crucial role in the toxicity. Finally, the results suggest that the treatment performed on the coal waste was efficient, even though significant toxicity have still been detected in the treated waste and additional steps are still required for adequate final disposal.

Semiquantitative determination of total mercury in Pygocentrus nattereri Kner, 1858 and sediment at the plateau of Upper Paraguai River, Brazil.

In this study an environmental assessment of contamination by total mercury (THg) was carried out at the Plateau of the Upper Paraguai River. Total mercury was evaluated in sediment and muscle of the red piranha Pygocentrus nattereri Kner, 1858, a piscivorous species at the top of the food chain consumed for subsistence and commercially. THg concentrations were below national guidelines established by WHO for sediments (100 ng g-1) and fish (100-600 ng g-1) for most of the sampled sites. Two sites located downstream of artisanal diamond and gold mines had THg concentrations in fish equal or greater than 600 ng g-1.

Evaluation of mercury pollution in cultivated and wild plants from two small communities of the Tapajós gold mining reserve, Pará State, Brazil.

This study examines the total Hg contamination in soil and sediments, and the correlation between the total Hg concentration in soil and vegetables in two small scale gold mining areas, São Chico and Creporizinho, in the State of Para, Brazilian Amazon. Total Hg values for soil samples for both study areas are higher than region background values (ca. 0.15 mg/kg). At São Chico, mean values in soils samples are higher than at Creporizinho, but without significant differences at alpha<0.05 level. São Chico's aboveground produce samples possess significantly higher values for total Hg levels than samples from Creporizinho. Creporizinho's soil-root produce regression model were significant, and the slope negative. Creporizinho's soil-aboveground and root wild plants regression models were also significant, and the slopes positives. Although, aboveground:root ratios were >1 in all of São Chico's produce samples, soil-plant parts regression were not significant, and Hg uptake probably occurs through stomata by atmospheric mercury deposition. Wild plants aboveground:root ratios were <1 at both study areas, and soil-plant parts regressions were significant in samples of Creporizinho, suggesting that they function as an excluder. The average total contents of Hg in edible parts of produces were close to FAO/WHO/JECFA PTWI values in São Chico area, and much lower in Creporizinho. However, Hg inorganic small gastrointestinal absorption reduces its adverse health effects.

Avaliação dos efeitos tóxicos em organismo aquático e terrestre expostos a elementos do grupo dos lantanídeos / Evaluation of toxic effects in aquatic and terrestrial organ-isms exposed to elements of the lanthanide group

A utilização dos elementos terras raras (ETR) em produtos de alta tecnologia, na medicina e na agricultura, a possibilidade de contaminação ambiental em todo seu ciclo de vida, por possuírem baixa mobilidade, os levam a ser considerados como contaminantes emergentes. O estudo avaliou a literatura sobre a ecotoxicologia terrestre dos ETR utilizando a base de dados Web of Science e a toxicidade aguda de três lantanídeos sobre a sobrevivência de Daphnia similis e germinação de sementes de Lactuca sativa. O efluente sintético utilizado foram nitratos de samário (Sm), lantânio (La) e neodímio (Nd), individualmente e em misturas binárias e ternárias em proporções volume/volume e identificados os tipos de interação. Os resultados foram apresentados em forma de um artigo e dois manuscritos. No artigo a maioria dos estudos foi realizada com espécies vegetais, com poucos sobre invertebrados. Lantânio e cerio foram os mais estudados. Efeitos controversos foram encontrados para as plantas, aplicações agronômicas não afetarão as plantas em baixas doses, mas podem afetar invertebrados do solo. No manuscrito com D. similis foi utilizado o meio MS, e o meio MSq, sem os quelantes EDTA e cianocobalamina, empregados para comparar seus efeitos na toxicidade dos ETR. Em MS individualmente a toxicidade decresceu de La > Sm > Nd e em MSq foi invertida, com toxicidade maior do que em MS. Os valores das CE50 individuais em MSq foram menores do que em MS, nas misturas binárias e nas ternárias, indicando que aparentemente os quelantes podem diminuir a biodisponibilidade dos ETR para os organismos teste. As interações observadas foram aditivas > sinérgicas > antagônicas. No segundo manuscrito foi estudado os efeitos de germinação, biomassa úmida e porcentagem de inibição da germinação (%IG) sobre a germinação de sementes de alface em dois substratos, um artificial (SA) e outro natural (argissolo vermelho amarelo, PVA). O parâmetro biomassa úmida (CI50), se mostrou mais sensível que germinação (CE50). Foi observado toxicidade nas maiores concentrações teste em relação ao controle nos dois substratos. A CE50 em SA foi menos tóxica do que em PVA, exceto na mistura binária Sm + Nd em PVA onde foram menos tóxicas. A diferença de toxicidade entre as proporções das misturas parecem estar associadas ao dobro de um dos elementos, tanto na germinação como na biomassa úmida. A categorização dos índices de %IG (NT não tóxica, MT moderadamente tóxica e FT fortemente tóxica) pode ser um alerta para a antecipação de eventos mais severos para os tomadores de decisão quanto as concentrações onde se inicia a toxicidade.

Avaliação dos efeitos tóxicos em organismo aquático e terrestre expostos a elementos do grupo dos lantanídeos / Evaluation of toxic effects in aquatic and terrestrial organ-isms exposed to elements of the lanthanide group

A utilização dos elementos terras raras (ETR) em produtos de alta tecnologia, na medicina e na agricultura, a possibilidade de contaminação ambiental em todo seu ciclo de vida, por possuírem baixa mobilidade, os levam a ser considerados como contaminantes emergentes. O estudo avaliou a literatura sobre a ecotoxicologia terrestre dos ETR utilizando a base de dados Web of Science e a toxicidade aguda de três lantanídeos sobre a sobrevivência de Daphnia similis e germinação de sementes de Lactuca sativa. O efluente sintético utilizado foram nitratos de samário (Sm), lantânio (La) e neodímio (Nd), individualmente e em misturas binárias e ternárias em proporções volume/volume e identificados os tipos de interação. Os resultados foram apresentados em forma de um artigo e dois manuscritos. No artigo a maioria dos estudos foi realizada com espécies vegetais, com poucos sobre invertebrados. Lantânio e cerio foram os mais estudados. Efeitos controversos foram encontrados para as plantas, aplicações agronômicas não afetarão as plantas em baixas doses, mas podem afetar invertebrados do solo. No manuscrito com D. similis foi utilizado o meio MS, e o meio MSq, sem os quelantes EDTA e cianocobalamina, empregados para comparar seus efeitos na toxicidade dos ETR. Em MS individualmente a toxicidade decresceu de La > Sm > Nd e em MSq foi invertida, com toxicidade maior do que em MS. Os valores das CE50 individuais em MSq foram menores do que em MS, nas misturas binárias e nas ternárias, indicando que aparentemente os quelantes podem diminuir a biodisponibilidade dos ETR para os organismos teste. As interações observadas foram aditivas > sinérgicas > antagônicas. No segundo manuscrito foi estudado os efeitos de germinação, biomassa úmida e porcentagem de inibição da germinação (%IG) sobre a germinação de sementes de alface em dois substratos, um artificial (SA) e outro natural (argissolo vermelho amarelo, PVA). O parâmetro biomassa úmida (CI50), se mostrou mais sensível que germinação (CE50). Foi observado toxicidade nas maiores concentrações teste em relação ao controle nos dois substratos. A CE50 em SA foi menos tóxica do que em PVA, exceto na mistura binária Sm + Nd em PVA onde foram menos tóxicas. A diferença de toxicidade entre as proporções das misturas parecem estar associadas ao dobro de um dos elementos, tanto na germinação como na biomassa úmida. A categorização dos índices de %IG (NT não tóxica, MT moderadamente tóxica e FT fortemente tóxica) pode ser um alerta para a antecipação de eventos mais severos para os tomadores de decisão quanto as concentrações onde se inicia a toxicidade.

Disposição continental de sedimentos de dragagem em solos tropicais: avaliação do risco ecológico de metais baseada em bioensaios com organismos aquáticos e edáficos / Disposal of dredged sediments in tropical soils: metal ecological risk assessment based on bioassays with aquatic and edaphic organisms

A ecotoxicidade associada à disposição continental de sedimentos de dragagem (oriundo da Baía de Guanabara, Rio de Janeiro) em latossolos e chernossolos foi estudada através de bioensaios agudos com o cladócero Daphnia similis e o oligoqueta Eisenia andrei; e de bioensaios crônicos com a alga doce Pseudokirchneriella subcaptata. Os teores de metais no dragado estavam acima dos preconizados pela legislação brasileira para disposição de materiais dragados. Os bioensaios empregados sugerem níveis maiores de toxicidade para as misturas de latossolo:dragado, em comparação aos tratamentos de chernossolo:dragado. No caso do chernossolo, a abundância de argilominerais 2:1, associada à alta fertilidade, parece ser capaz de reduzir a ecotoxicidade potencial. Em latossolo, mesmo as menores dosagens de aplicação de sedimento (3,33 e 6,66%) foram capazes de provocar efeitos adversos significativos aos microcrustáceos e às algas. Em misturas de chernossolo, efeitos significativos foram observados somente para doses de 6,58 e 13,16% para microcrustáceos e algas, respectivamente. Tais dados indicaram a ocorrência potencial de risco ecotoxicológico para as comunidades aquáticas vizinhas em cenários em que solos misturados com materiais dragados pudessem ser lixiviados e soluções tóxicas atingissem sistemas fluviais vizinhos. O ensaio agudo de papel de contato com E. andrei também acusou a ocorrência potencial de efeitos adversos sobre a fauna edáfica, a partir das doses de 13,12 e 19,74% em latossolo e chernossolo, respectivamente. O emprego do referido ensaio parece ser extremamente promissor no monitoramento da ecotoxicidade potencial de solos impactados pela disposição de resíduos sólidos e/ou contaminados por metais.

Potential ecotoxicity associated with the disposal of dredged sediments (from the Guanabara Bay, Rio de Janeiro, Brazil) in ferralsols and chernosols was studied through acute bioassays with micro-crustaceans (Daphnia similis) and earthworms (Eisenia andrei); and through chronic assays with algae (Pseudokirchenriella subcaptata). Total metal concentrations in the sediment were higher than the limits established by Brazilian legislation for dredged sediment disposal. The bioassays suggest the occurrence of more significant effects on ferralsols mixtures compared to chernosols treatments. In chernosol mixtures, the abundance of 2:1 clay minerals is apparently able to reduce the ecotoxicity. In ferralsol mixtures, lower dosages of sediment application (3.33 and 6.66%) caused significant effects on micro-crustaceans and algae. In chernosol treatments, adverse effects on in micro-crustaceans and algae were only observed for the doses of 6.58 and 13.16%, respectively. Such data indicate occurrence of potential risks on aquatic biota in the scenario where sediment-amended soils could be leached and such solutions could contaminate surrounding fluvial systems. The bioassay with E. andrei using contact paper also suggests the occurrence of potential adverse effects on edaphic biota. In addition, such tests with E. andrei demonstrate that they are highly applicable as alternative tools to monitor potential ecotoxicity associated with terrestrial disposal of solid residues containing domestic wastes and/or contaminated with metals.