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The demand for rare earth elements (REEs) is growing and as a result, environmental exposure is a concern. The objective of this research was to evaluate the acute toxicity of Tm to Hyalella azteca and to understand the potential for toxicity modification by dissolved organic matter (DOM) and the cations Ca2+, Mg2+ and Na+. Standard methods were followed for 96 h static exposures in a medium with a hardness of 60 mg CaCO3/L, pH of 7.3 at 23 °C. H. azteca neonates (2-9 d of age) were used and in unmodified media the LC50 concentration was 3.4 µM [95% CI 2.9-3.9 µM; 573 µg/L (482-663)] based on measured dissolved concentrations at the end of the test. Tests done with different concentrations of Ca (0.25, 0.5 and 1.5 mM) did not show consistent trends and there was no clear evidence of a protective effect from Ca. Variations in Na (0.26, 0.5 and 1.6 mM) resulted in no significant changes in toxicity. Similarly, Mg (0.07, 0.14 and 0.4 mM) did not result in significant changes in LC50 values, except for a reduction in toxicity for measured total Tm at the lowest Mg concentration. Our results indicate that Tm toxicity is not influenced by cationic competition (Ca, Na and Mg). Dissolved organic matter (sourced from Luther Marsh ON) offered significant protection against Tm toxicity. Addition of 9 mg DOC/L resulted in significantly increased LC50 values. This study contributes toward understanding the toxicity of Tm and the importance of considering dissolved organic matter in estimating the potential for environmental risk of REEs.

Dissolved Ni concentrations inhibiting the growth of juvenile great pond snails (Lymnaea stagnalis) have been documented to vary from about 1 to 200 µg L-1 Ni. This variability makes L. stagnalis either a moderately sensitive or the most sensitive freshwater species to chronic Ni exposure tested to date. Given the role of sensitive species in environmental risk assessment frameworks, it is particularly important to understand this variability, i.e., to characterize the factors that modulate Ni toxicity and that may confound toxicity test outcomes when uncontrolled. In the present study, we tested if this variability was due to analytical (growth calculation: biomass versus growth rate), environmental (water quality), lab-specific practices, and/or snail population differences among earlier studies. Specifically, we reanalyzed previously published Ni toxicity data and conducted additional measurements of Ni aqueous speciation, short-term Ni uptake, and chronic Ni toxicity with test waters and snail cultures used in previous studies. Corrections for Ni bioavailability and growth calculations explained a large degree of variability in the published literature. However, a residual 16-fold difference remained puzzling between 2 studies: Niyogi et al. (2014) (low ECxs) and Cremazy et al. (2018) (high ECxs). Indeed, differences in metal bioavailability due to water chemistry, lab-specific practices, and snail population sensitivity could not explain the large variation in Ni toxicity in these 2 very similar studies. Other potentially important toxicity-modifying factors were not directly evaluated in the present work: test duration, diet, snail holding conditions, and snail age at onset of testing. The present analysis highlights the need for further studies to elucidate 1) the mechanisms of growth inhibition in Ni-exposed L. stagnalis and 2) the important abiotic and biotic factors affecting this biological response. Until these processes are understood, substantial uncertainties will remain about inclusion of this species in Ni environmental risk assessment. Integr Environ Assess Manag 2020;16:983-997. © 2020 SETAC.

The demand for rare earth elements (REEs) is growing and as a result, environmental exposure is a concern. The objective of this research was to evaluate the acute toxicity of Tm to Hyalella azteca and to understand the potential for toxicity modification by dissolved organic matter (DOM) and the cations Ca2+, Mg2+ and Na+. Standard methods were followed for 96 h static exposures in a medium with a hardness of 60 mg CaCO3/L, pH of 7.3 at 23°C. H azteca neonates (2-9 d of age) were used and in unmodified media the LC50 concentration was 3.4 µM (95% CI 2.9-3.9 µM; 573 µg/L (482-663)) based on measured dissolved concentrations at the end of the test. Tests done with different concentrations of Ca (0.25, 0.5 and 1.5 mM) did not show consistent trends and there was no clear evidence of a protective effect from Ca. Variations in Na (0.26, 0.5 and 1.6 mM) resulted in no significant changes in toxicity. Similarly, Mg (0.07, 0.14 and 0.4 mM) did not result in significant changes in LC50 values, except for a reduction in toxicity for measured total Tm at the lowest Mg concentration. Our results indicate that Tm toxicity is not influence by cationic competition (Ca, Na and Mg). Dissolved organic matter (sourced from Luther Marsh ON) offered significant protection against Tm toxicity. Additions over 3 mg DOC/L resulted in significantly increased LC50 values. This study contributes toward understanding the toxicity of Tm and the importance of considering dissolved organic matter in estimating the potential for environmental risk of REEs.

Dissolved organic carbon (DOC) is known to ameliorate the toxicity of the trace metal nickel (Ni) to aquatic animals. In theory, this effect is mediated by the capacity of DOC to bind Ni, rendering it less bioavailable, with the resulting reduction in accumulation limiting toxicological effects. However, there is a lack of experimental data examining Ni accumulation in marine settings with natural sources of DOC. In the current study, radiolabelled Ni was used to examine the time- and concentration-dependence of Ni accumulation, using naturally sourced DOC, on developing larvae of the sea urchin Strongylocentrotus purpuratus. Contrary to prediction, the two tested natural DOC samples (collected from the eastern United States, DOC 2 (Seaview park, Rhode Island (SVP)) and DOC 7 (Aubudon Coastal Center, Connecticut)) which had previously been shown to protect against Ni toxicity, did not limit accumulation. The control (artificial seawater with no added DOC), and the DOC 2 sample could mostly be described as having saturable Ni uptake, whereas Ni uptake in the presence of DOC 7 was mostly linear. These data provide evidence that DOC modifies the bioavailability of Ni, through either indirect effects (e.g. membrane permeability) or by the absorption of DOC-Ni complexes. There was some evidence for regulation of Ni accumulation in later-stage embryos (96-h) where the bioconcentration factor for Ni declined with increasing Ni exposure concentration. These data have implications for predictive modelling approaches that rely on known relationships between Ni speciation, bioavailability and bioreactivity, by suggesting that these relationships may not hold for natural marine DOC samples in the developing sea urchin model system.

The Windermere Humic Aqueous Model (WHAM) is often used for risk assessment of metals; WHAM can be used to estimate the potential bioavailability of dissolved metals, where metals complexed to dissolved organic matter (DOM) are expected to be less toxic than ionic forms. Silver is a potential metal of concern but WHAM has not been rigorously tested against experimental measurements. This study compares WHAM predictions to measured ionic silver during fixed pH (4, 8 or 10) argentometric titrations of DOM from diverse origins. There were almost two orders of magnitude variation in free silver between sources but, within model uncertainty, WHAM captured this variability. This agreement, between measurements and models, suggests that WHAM is an appropriate tool for silver risk assessment in surface receiving waters when DOM is predominantly in the form of humic/fulvic acids. In sewage samples WHAM dramatically underestimated silver binding by approximately 3 orders of magnitude. Simulations with additional specific strong silver binding sulphide-like binding sites could explain Ag binding at low loadings, but not at higher loadings. This suggests the presence of additional intermediate strength binding sites. These additional ligands would represent components of the raw sewage largely absent in natural waters unimpacted by sewage effluents. A revised empirical model was proposed to account for these sewage-specific binding sites. Further, it is suspected that as sewage organic matter is degraded, either by natural attenuation or by engineered treatment, that sewage organic matter will degrade to a form more readily modelled by WHAM; i.e., humic-like substances. These ageing experiments were performed starting from raw sewage, and the material did in fact become more humic-like, but even after 30 days of aerobic incubation still showed greater Ag+ binding than WHAM predictions. In these incubation experiments it was found that silver (up to 1000 μg/L) had minimal impact on ammonia oxidation kinetics.

Soil organic matter (SOM) is known to exert a major control on the mobility and bioavailability of cationic nutrients. However, the role of SOM in the fate of anionic nutrients, especially phosphorus (P), is less well characterized. The objectives of this study were to (1) compare the formation of binary complexes of calcium (Ca) with humic acids (HA) extracted from two contrasting soils, and (2) determine if binary HA-Ca complexes could incorporate P by forming ternary HA-Ca-P complexes. The Ca binding capacities of the HA extracted from an agricultural organic soil (AOS) and a pristine riparian soil (RS) were measured via potentiometric titrations; the formation of ternary complexes was analyzed by size fractionation using MWCO tubes. Proton and Ca binding capacities of RS-HA were higher than AOS-HA, and pH had a weaker effect on Ca binding to RS-HA. These differences are consistent with lower proportions of aromatic groups, and a higher proportion of alkyl groups derived from 13C NMR spectroscopy. Together, the NMR, titration and MWCO data indicate that Ca binds to RS-HA through monodentate complexes and electrostatic attraction that are capable of binding P producing ternary complexes. In contrast, at pH 8.5 Ca forms bidentate complexes with AOS-HA, which do not provide bridging positions to incorporate P. Overall, our results imply that the formation of HA-Ca and HA-Ca-P complexes depend on the structure of the HA, and that complexation to HA may play an important role in the fate of P in terrestrial and aquatic environments.

The Conditional Affinity Spectrum (CAS) is essential for describing the binding site heterogeneity of natural organic matter. A numerical method called ‘Fully Optimized ContinUouS’ (FOCUS) is described and employed to determine the CAS of H and Pb binding to Suwannee River Humic Acid (SRHA). The FOCUS-CAS is compared with the analytical solution of CAS based on the fitting of the experimental data to the Non-Ideal Competitive Adsorption (NICA) model. Although both methods give satisfactory results, their CAS distribution features are different, indicating that different CAS can reproduce the binding data at similar level of goodness-of-fit. Within a comparable, but not identical, affinity range, the FOCUS-CAS shows multimodal distributions, whereas the NICA-CAS displays bimodal distributions. These differences are due to the fact that the NICA-CAS assumes an a priori functionality (i.e., carboxylic and phenolic), while the FOCUS-CAS does not make this assumption. Without knowing the chemical reality of the binding site explicitly, both methods are viable. The NICA-CAS is theoretically superior to the FOCUS-CAS because it provides informative descriptions of competition between the H- and Pb-binding. Nonetheless, the FOCUS-CAS is practically more convenient because it does not require proton binding data. Additionally, the FOCUS-CAS can describe some strong metal-binding sites (e.g., thiol) that cannot be described by the NICA-CAS and, thus, constitutes a suitable alternative to NICA-CAS.

Nickel (Ni) emissions resulting from production and transportation raise concerns about the impact of Ni exposure to marine ecosystems. Ni bioavailability models are established for FW systems, but the influence of chemical parameters (e.g. dissolved organic carbon (DOC)) on Ni toxicity within marine systems is less well understood. To examine the effects of DOC concentration and composition on Ni toxicity, acute toxicity tests were conducted on early life-stages of blue mussels (Mytilus edulis) and sea urchin embryos (Strongylocentrotus purpuratus) in full strength sea water (32 ppt). Nine different field collected samples of water with varying concentration (up to 4.5 mg C/L) and composition of DOC were collected from the east coast of the United States. Organic matter compositional analysis included molecular fluorescence and absorbance spectroscopy. The different DOC sources had different protective effects against embryo toxicity. The control (no DOC) Ni 48 h-EC50 for Mytilus embryos was 133 µg/L (95% confidence interval (C.I.) of 123–144 µg/L), while Strongylocentrotus embryos displayed control 96-h EC50 values of 207 µg/L (167–247 µg/L). The most significantly protective sample had high humic acid concentrations (as determined from fluorescence spectroscopy), which yielded an EC50 of 195 µg/L (169–222 µg/L) for Mytilus, and an EC50 of 394 µg/L (369–419 µg/L) for S. purpuratus. Among all samples, protection was related to both DOC quantity and quality, with fluorescence-resolved humic and fulvic acid concentrations showing the strongest correlations with protection for both species. These data suggest that DOC is protective against Ni toxicity in M. edulis and S. purpuratus, and that accounting for a DOC quality factor will improve predictive toxicity models such as the biotic ligand model.

The aim of the present study was to determine the influence of salinity and organism age on the chronic toxicity of waterborne lead (Pb) to Atherinops affinis and to compare the relative Pb sensitivity of A. affinis with other marine species. Chronic Pb exposure experiments were conducted in a water flow-through testing system. Survival, standard length, dry weight, and tissue Pb concentration were measured and lethal concentrations (LCs), effect concentrations (ECs), and bioconcentration factors (BCFs) were calculated. In general, increasing salinity and organism age decreased Pb toxicity. The LC50s for larval fish at 14 and 28 ppt salinity were 15.1 and 79.8 μg/L dissolved Pb, respectively; whereas, the LC50 for juvenile fish was 167.6 μg/L dissolved Pb at 28 ppt salinity. Using standard length data, the EC10 values for larval fish were 16.4 and 82.4 μg/L dissolved Pb at 14 and 28 ppt salinity, respectively. The dry weight EC25s for low and high salinity were 15.6 and 61.84 μg/L dissolved Pb, respectively. The BCFs were higher with the lower salinity study (1703) in comparison to the higher salinity study (654). Results of Pb speciation calculation showed higher fraction of Pb2+ in water with lower salinity, explaining the higher observed toxicity of Pb in lower salinity water than higher salinity water. Atherinops affinis is more sensitive to Pb than several other marine species. Evidence of abnormal swimming and skeletal deformities were observed in Pb exposure treatments. Results of the present study are useful for marine biotic ligand modeling and support ecological risk assessment and deriving Pb environmental quality criteria for marine environments. Environ Toxicol Chem 2018;37:2705-2713. © 2018 SETAC.

Made available in DSpace on 2018-12-11T16:53:53Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-09-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado do Amazonas Natural Sciences and Engineering Research Council of Canada Dissolved organic carbon (DOC) represents a heterogeneous group of naturally-occurring molecules in aquatic environments, and recent studies have evidenced that optically dark DOCs can exert some positive effects on ionoregulatory homeostasis of aquatic organisms in acidic waters. We investigated the effects of Luther Marsh DOC, a dark allochthonous DOC, on ion regulation and N-waste excretion of zebrafish acutely exposed to either neutral or low pH in ion-poor water. In the first experiment, simultaneous exposure to pH 4.0 and DOC greatly attenuated the stimulation of Na+ diffusive losses (Jout Na), and prevented the blockade of Na+ uptake (Jin Na) seen in zebrafish exposed to pH 4.0 alone, resulting in much smaller disturbances in Na+ net losses (Jnet Na). DOC also attenuated the stimulation of net Cl− losses (Jnet Cl) and ammonia excretion (Jnet Amm) during acidic challenge. In the second experiment, zebrafish acclimated to DOC displayed similar regulation of Jin Na and Jout Na, and, therefore, reduced Jnet Na at pH 4.0, effects which persisted even when DOC was no longer present. Protective effects of prior acclimation to DOC on Jnet Cl and Jnet Amm at pH 4.0 also occurred, but were less marked than those on Na+ balance. Urea fluxes were unaffected by the experimental treatments. Overall, these effects were clearly beneficial to the ionoregulatory homeostasis of zebrafish at low pH, and were quite similar to those seen in a recent parallel study using darker DOC from the upper Rio Negro. This suggests that dark allochthonous DOCs share some chemical properties that render fish tolerant to ionoregulatory disturbances during acidic challenge. Laboratory of Ecophysiology and Molecular Evolution Brazilian National Institute for Research of the Amazon Department of Biology McMaster University Department of Zoology University of British Columbia Department of Chemistry and Biochemistry Wilfrid Laurier University Biosciences Institute São Paulo State University (UNESP), Coastal Campus, Pça Infante Dom Henrique s/n°, P.O. Box 73601 Biosciences Institute São Paulo State University (UNESP), Coastal Campus, Pça Infante Dom Henrique s/n°, P.O. Box 73601 CNPq: 151083/2013-4 CNPq: 401303/2014-4

Speciation of copper in marine systems strongly influences the ability of copper to cause toxicity. Natural organic matter (NOM) contains many binding sites which provides a protective effect on copper toxicity. The purpose of this study was to characterize copper binding with NOM using fluorescence quenching techniques. Fluorescence quenching of NOM with copper was performed on nine sea water samples. The resulting stability constants and binding capacities were consistent with literature values of marine NOM, showing strong binding with $$\log K$$ values from 7.64 to 10.2 and binding capacities ranging from 15 to 3110 nmol mg $${\text {C}}^{-1}.$$ Free copper concentrations estimated at total dissolved copper concentrations corresponding to previously published rotifer effect concentrations, in the same nine samples, were statistically the same as the range of free copper calculated for the effect concentration in NOM-free artificial seawater. These data confirms the applicability of fluorescence spectroscopy techniques for NOM and copper speciation characterization in sea water and demonstrates that such measured speciation is consistent with the chemical principles underlying the biotic ligand model approach for bioavailability-based metals risk assessment.

Light energy and oxygen drive photo-oxidation of dissolved organic carbon (DOC). The longer the wavelength the greater its depth of penetration into water, changing the spectral environment with depth. We asked how oxygen concentration and light spectral composition might affect photo-oxidation processes in DOC. Outdoor experiments compared responses of fluorescence and absorbance indices to photo-oxidation of filtered (0.45 µm) Rio Negro water (Amazon Basin) under near-anoxia, normoxia and hyperoxia exposed to natural sunlight or reduced sunlight (≥340, reduced-UVR). Near-anoxia decreased all absorbance and fluorescence indices. Absorbance changed across the spectrum (≥250 nm) even under reduced-UVR provided that oxygen was present. This phenomenon maintains broader photo-oxidation and the release of CO2 at depth. Slope350–400 was responsive to changes in the irradiance field but not to oxygen concentration, while Slope275–295 responded to both. Thus, larger molecules are broken down near the water's surface and medium to smaller molecules continue to be processed at depth. The production of fulvic acid-like fluorescence required both UVB and oxygen, restricting its production to surface waters. The relatively small increase in R254/365 compared with the loss of SUVA254 under near-anoxia indicated a slower breakdown of larger DOC molecules as oxygen becomes limiting. Breakdown of larger molecules which absorb in the 350–400 nm range, appears to involve two steps – one by radiant energy and another involving oxygen. The study results reflect the dynamic gradients in photo-oxidation with depth.

We evaluated the effects of varying water chemistry ([Ca2+]=0.2-3mM, [Mg2+]=0.05-3mM, dissolved organic matter (DOM, natural, from maple leaves)=0.3-10mg of CL-1, pH=5.0-8.5) on the acute (96-h, unfed fish) and chronic (30-d, fed fish) toxicity of waterborne Cu to juvenile rainbow trout (Oncorhynchus mykiss) exposed in flow-through conditions. Acute and chronic Biotic Ligand Models (BLMs) were developed from the obtained toxicity data-sets, using the Visual MINTEQ software. Our results indicate that Cu is predominantly an acute toxicant to rainbow trout, as there were no observable growth effects and the 96-h and 30-d LC50 values were similar, with mortality mostly occurring within the first few days of exposure. Calcium and DOM were greatly protective against both acute and chronic Cu toxicity, but Mg seemed to only protect against chronic toxicity. Additional protection by pH 5.0 in acute exposure and by pH 8.5 in chronic exposure occurred. In the range of conditions tested, the observed 96-h LC50 and 30-d LC20 values varied by a factor of 39 and 27 respectively. The newly developed acute and chronic BLMs explained these variations reasonably well (i.e. within a 2-fold error), except at pH≥8 where the high observed acute toxicity could not be explained, even by considering an equal contribution of CuOH+ and Cu2+ to the overall Cu toxicity. The 96-h LC50 values of 59% of 90 toxicity tests from 19 independent studies in the literature were reasonably well predicted by the new acute BLM. The LC20 predictions from the new chronic BLM were reasonable for 7 out of 14 toxicity tests from 6 independent chronic studies (with variable exposure durations). The observed deviations from BLM predictions may be due to uncertainties in the water chemistry in these literature studies and/or to differences in fish sensitivity. A residual pH effect was also observed for both the acute and the chronic data-sets, as the ratio of predicted vs. observed LC values generally increased with the pH. Additional mechanistic studies are required to understand the influence of pH, Na, and Mg on Cu toxicity to trout. The present study presents the first experimentally developed chronic Cu BLM for the rainbow trout. To the best of our knowledge, it also presents the first acute Cu BLM that is based on a published data-set for trout. These newly developed BLMs should contribute to improving the risk assessment of Cu to fish in freshwater.

The effects of pH, metal ions (i.e. Cu2+, Cd2+, Pb2+ and Zn2+) and natural organic matter (i.e. Suwannee River natural organic matter standard [SRNOM]) on determination of thiol (i.e. reduced glutathione [GSH]) by cathodic stripping voltammetry were evaluated. pH was the most critical parameter to influence GSH voltammogram (i.e. peak shape, position and height). In presence of Cu and Cd, secondary peaks were found at [metal]/GSH > 1 due to formation of GSH complexes at pH = 8.0 (Cu and Cd) and 2.5 (Cu only). On the other hand, Pb showed negligible influence on GSH voltammogram at pH 8.0 and 2.5 within [Pb]/[GSH] = 0.01–2.0. Zn significantly reduced GSH peak height at pH 2.5 at [Zn]/[GSH] = 0.01–2.0. SRNOM peak significantly overlapped with GSH peak at pH 8.0 and [SRNOM] > 1 mg L−1 but was clearly separated from the GSH peak at pH 2.5. However, at pH 2.5, the presence of metal ions and/or SRNOM significantly underestimated GSH concentration (recovery = 21–69%), likely due to metal complexation wit...

Copper at high concentrations is an ionoregulatory toxicant in fish and its toxicity is known to be strongly modulated by the water chemistry. The toxicity of Cu to the tropical fish cardinal tetra (Paracheirodon axelrodi) was investigated in waters from two major rivers of the Amazon watershed: the Rio Negro (filtered0.45μm, pH 5.6, DOC=8.4 mgL

Given the reported degraded nature of DOC in the Rio Negro, and low oxygen, pH, and bacterial riverine levels, we hypothesized: (1) DOC would have strong humic and fulvic acid fluorescence signals with high aromaticity and large mean molecular weight; and (2) photo-oxidation rates would be slow, and reactive oxygen species (ROS) concentrations low, producing no oxidative stress in biota. We surveyed the environment and properties of DOC and explored DOC photo-oxidation and fish sensitivity to DOC products. DOC properties were investigated using absorption and fluorescence indices and parallel factor analysis (PARAFAC) of excitation–emission matrices. ROS concentrations were measured spectrophotometrically. A native fish, Hemigrammus levis, was exposed to photo-oxidizing DOC and its tissues (brain, gill, liver) assayed for changes in antioxidant and biotransformation enzymes. With respect to our hypotheses, (1) DOC was highly terrigenous, with high SAC340 values (aromaticity), high capacity to produce ROS, and high tryptophan-like fluorescence (bacterial, autochthonous signal); (2) photo-oxidation rates were appreciable, while products were related to mean UV-radiation levels (total radiation was constant). ROS levels were often higher than freshwater averages, yet fish experienced no oxidative stress. Results suggest photo-oxidation influences patterns in C-cycling, bacterial production and community dynamics between wet and dry seasons.

Non-reactive phosphorus (nRP) contains condensed phosphates and organic phosphorus (OP) species that are recalcitrant in secondary wastewater treatment and tend to remain in final effluents. To meet ultra-low effluent P discharge limits, persistent nRP must be removed. The objective of this study was to evaluate the use of an advanced oxidation process (AOP) which couples TiO2/UV photolysis with ultrafiltration to oxidize and remove nRP species. Initial tests utilized OP model compounds, adenosine triphosphate (ATP) and aminoethylphosphonate (AEP), in a binary mixture to evaluate AOP treatment and to elucidate possible mechanisms of phosphorus removal. The results were consistent with a model of preferential ATP binding to the TiO2 surface compared to AEP. On UV light exposure, AEP was removed from solution due to the photooxidation of ATP freeing up binding sites for AEP adsorption and subsequent oxidation. Orthophosphate released during AOP treatment was retained on the TiO2 solids. The AOP was applied to three municipal wastewaters and one automotive industry effluent for P removal. In all cases, phosphorus removal was found to occur through filtration, surface complexation and UV oxidation. Total phosphorus removal efficiencies between 90 and 97% were observed for the municipal wastewater effluents and 44% removal was observed in the industrial effluent after treatment using AOP.

Systems rich in terrigenous dissolved organic carbon (DOC), like the Rio Negro, can contribute significant amounts of carbon dioxide back to the atmosphere and support important microbial communities. We investigated photo-oxidation in the Rio Negro: (1) the depth to which light causes complete photo-oxidation to CO2 and changes in DOC structure, (2) the daily rate of change of absorbance indices, (3) the relationship between sub-surface rates of photo-oxidation to CO2 and light exposure, (4) the areal rates of photo-oxidation, and (5) the stability of fluorophore signals. Experiments were run in an outdoor pool of Rio Negro water, under natural sunlight during the dry seasons of 2015 and 2018. In 2018, rates of complete photo-oxidation and changes in absorbance indices decayed exponentially, approaching their asymptotes between 9 and 15 cm depth. In 2015, direct absorbance indices ceased changing at 14 cm depth. Fluorescence of humic acid-like moieties continued to decrease, sometimes to 35–43 cm depth. This indicates that partial photo-oxidation of DOC, and thus interaction with the microbial community, occurs to greater depths than previously expected. Areal rates of CO2 production were 28.8 and 39.3 mg C m−2 d−1 (two experiments, October 2018). Sub-surface (1.1 cm) rates were strongly related to light levels, reaching a maximum of 0.68 mg C l−1 d−1 in September. Complete photo-oxidation ceased below 29.6 mW cm−2 d−1 UV radiation, providing a daily baseline for observable production of CO2. Absorbance indices changed by 9 to 14% d−1 at high light levels, except for R254/365 (4.4% d−1). Fluorophore emission ranges were stable between 2014 and 2018, indicating that emissions can be compared across time and space. This study contributes to better estimates and understanding of photo-oxidation in tropical, black-water rivers, which will be useful for carbon modelling. © 2020 Elsevier B.V.

Acute copper (Cu) toxicity tests (48-h LC50) using the euryhaline rotifer Brachionus plicatilis were performed to assess the effects of salinity (3, 16, 30 ppt) and dissolved organic carbon (DOC, ∼ 1.1, ∼ 3.1, ∼ 4.9, ∼ 13.6 mg C L(-1)) on Cu bioavailability. Total Cu was measured using anodic stripping voltammetry, and free Cu(2+) was measured using ion-selective electrodes. There was a protective effect of salinity observed in all but the highest DOC concentrations; at all other DOC concentrations the LC50 value was significantly higher at 30 ppt than at 3 ppt. At all salinities, DOC complexation significantly reduced Cu toxicity. At higher concentrations of DOC the protective effect increased, but the increase was less than expected from a linear extrapolation of the trend observed at lower concentrations, and the deviation from linearity was greatest at the highest salinity. Light-scattering data indicated that salt induced colloid formation of DOC could be occurring under these conditions, thereby decreasing the number of available reactive sites to complex Cu. When measurements of free Cu across DOC concentrations at each individual salinity were compared, values were very similar, even though the total Cu LC50 values and DOC concentrations varied considerably. Furthermore, measured free Cu values and predicted model values were comparable, highlighting the important link between the concentration of bioavailable free Cu and Cu toxicity.

Biotic ligand models (BLMs) for metals are useful for risk assessment. The modeling of metal complexation by the biotic ligand has received little attention relative to the modeling of organic and inorganic complexation of metals in solution. We used ion selective electrodes (ISEs) to directly characterize copper and silver binding to rainbow trout gill cells, either as cultured reconstructed epithelia, or dispersed in suspension. Preparations were composed of pavement cells (PVCs) alone or mixtures of PVCs (≈85%) and mitochondria-rich cells (MRCs, ≈15%). Mixed cells showed up to an order of magnitude greater binding for both metals, indicating that MRCs were much more important than PVCs. Also, cell orientation had a dramatic effect; cells cultured as epithelia exhibited much greater binding than cells in suspension. Silver and copper demonstrated generally similar binding behavior, with stronger (logK ≈ 10 or greater) and weaker binding sites (logK ≈ 8). Comparisons to existing BLM calibrations show good agreement, but reveal that selection of analytical window can impact which binding sites are titrated. We conclude that cultured gill epithelia in vitro provide a powerful approach to studying metal complexation directly at the biotic ligand.

This study investigated the acute toxicity of nickel (Ni) to cardinal tetra (Paracheirodon axelrodi), within the three main water types of the Amazon basin: black (Rio Negro), white (Rio Solimoes) and clear (Rio Tapajos) during the wet and dry season at pH 7 (representative of white and clear rivers) and pH 4 (representative of black waters). The influence of dissolved organic carbon (DOC) quality on Ni toxicity within the three waters was also explored via the use of DOC isolates. Differences in water chemistry, DOC quality and ion concentrations were shown between waters and between seasons. Toxicity of Ni was shown to vary between river waters, seasons, and pHs. Ni was significantly less toxic during the dry season at pH 4 in all three river waters; for example, black water during the wet season had an LC50 of 9.72 mg Ni/L compared to 41.5 mg Ni/L during the dry season. At pH 7, contrasting effects in toxicity between seasons were shown between black and clear waters (black: wet = 28.9 mg/L, dry = 17.3 mg/L; clear: wet = 13.8 mg/L, dry = 24.1 mg/L). There were no significant differences in Ni toxicity for white waters at pH 7 (white: wet = 22.2 mg/L, dry = 21.8). Overall, Ni was shown to be more toxic at pH 7 than at pH 4 except in black water during the wet season. Toxicity of Ni at pH 4 was positively related to DOC concentration and amount of humic-like and fulvic-like DOC and negatively related to fluorescence index. Therefore, at pH 4, Ni is more toxic in waters containing more allochthonous DOC, consisting of higher amounts of humic-like and fulvic-like components. LC50 values for the different DOC concentrates at the same DOC concentration of 4.5 mg/L (black: 26.8 mg/L; white: 73.3 mg/L; clear: 49.2) support the river water findings at pH 4 (Ni more toxic in presence of black DOC) indicating that DOC quality alone can influence Ni toxicity at this pH.

Dissolved organic matter (DOM), a heterogeneous substance found in all natural waters, has many documented abiotic roles, but recently, several possible direct influences of DOM on organism physiology have been reported. However, most studies have been carried out with a limited number of natural DOM isolates or were restricted to the use of commercial or artificial humic substances. We therefore employed three previously characterized, chemically-distinct natural DOMs, as well as a commercially available humic acid (Aldrich, AHA), at circumneutral (7–8) and acidic pH (~ 5), to examine DOM effects on whole-body Na + concentration, unidirectional influx and efflux rates of Na + , and ammonia and urea excretion rates in Daphnia magna . Whole-body Na + concentration, Na + influx, and Na + efflux rates were all unaffected regardless of pH, suggesting no influence of the various natural DOMs on active uptake and passive diffusion of Na + in this organism. Ammonia and urea excretion rates were both increased by low pH. Ammonia excretion rates were reduced at circumneutral pH by the most highly colored, allochthonous DOM, and at low pH by all three natural DOMs, as well as by the commercial AHA. Urea excretion rates were not influenced by the presence of the various DOMs in circumneutral solutions, but were attenuated by the presence of two allochthonous DOM sources (isolated from Bannister Lake and Luther Marsh) at acidic pH. The observed reductions may be attributed partially to the higher buffering capacities of natural DOM sources, as well as their ability to interact with biological membranes as estimated by a new measure calculated from their acid–base titration characteristics, the Proton Binding Index (PBI).

Despite increasing institutional and financial support, certain public health issues are still neglected by the Chinese Government. The present paper examines the soil-transmitted helminth (STH) infection and reinfection rates by conducting a survey on 1724 children in Guizhou Province, China. Our results indicate that 37.5 percent of children had been infected with one or more of the three types of tested STH. However, only 50.4 percent of children reported having taken deworming medicine during the 18-month period before the survey. Of those who reported being dewormed, 34.6 percent tested positive for STH infections. Poverty and number of siblings are significantly and positively correlated with infection and reinfection, and parental education is significantly and negatively correlated with infection and reinfection. Given the ineffectiveness of treatment in these areas to date, for anthelminthic campaigns to actually succeed, China must pay more attention to local-level incentives to improve children's health.

Made available in DSpace on 2018-12-11T16:40:57Z (GMT). No. of bitstreams: 0 Previous issue date: 2016-02-08 The so-called â œ blackwatersâ of the Amazonian Rio Negro are rich in highly coloured dissolved organic carbon (DOC), but ion-poor and very acidic, conditions that would cause fatal ionoregulatory failure in most fish. However these blackwaters support 8% of the worldâ ™ s ichthyofauna. We tested the hypothesis that native DOC provides protection against ionoregulatory dysfunction in this extreme environment. DOCs were isolated by reverse-osmosis from two Rio Negro sites. Physico-chemical characterization clearly indicated a terrigenous origin, with a high proportion of hydroxyl and phenolic sites, high chemical reactivity to protons, and unusual proteinaceous fluorescence. When tested using zebrafish (a model organism), Rio Negro DOC provided almost perfect protection against ionoregulatory disturbances associated with acute exposure to pH 4.0 in ion-poor water. DOC reduced diffusive losses of Na + and Cl â', and promoted a remarkable stimulation of Na + uptake that otherwise would have been completely inhibited. Additionally, prior acclimation to DOC at neutral pH reduced rates of branchial Na + turnover, and provided similar protection against acid-induced ionoregulatory disturbances, even if the DOC was no longer present. These results reinforce the important roles that DOC molecules can play in the regulation of gill functions in freshwater fish, particularly in ion-poor, acidic blackwaters. Laboratory of Ecophysiology and Molecular Evolution National Institute for Amazonian Research Department of Chemistry and Biochemistry Wilfrid Laurier University Department of Biology McMaster University Department of Zoology University of British Columbia Biosciences Institute Saõ Paulo State University-UNESP Coastal Campus Biosciences Institute Saõ Paulo State University-UNESP Coastal Campus

A 96 h toxicity test showed that the embryos of the New Zealand sea urchin (Evechinus chloroticus) are the most sensitive of all studied marine species to waterborne nickel (Ni), with the EC50 for the development of fully formed pluteus larvae found to be 14 μg L(-1). Failure to develop a standard larval shape suggested skeletal impairment. Whole body ions (Na, Mg) increased with Ni exposure and calcium influx was depressed. The effects of natural organic matter (NOM) on Ni accumulation and toxicity were also examined in three different seawater sources (nearshore, offshore, and near the outlet of a "brown water" stream). At low dissolved organic carbon (DOC) concentrations the brown water NOM was protective against Ni toxicity, however at higher DOC concentrations it exacerbated developmental toxicity in the presence of Ni. These results show that sea urchin development is highly sensitive to Ni via a mechanism that involves ionoregulatory disturbance, and that Ni toxicity is influenced by environmental factors such as NOM. These data will be critical for the development of water quality guidelines for Ni in the marine environment.

Various quality predictors of seven different natural dissolved organic matter (DOM) and humic substances were evaluated for their influence on protection of Daphnia magna neonates against copper (Cu) toxicity. Protection was examined at 3 and 6 mg l(-1) of dissolved organic carbon (DOC) of each DOM isolate added to moderately hard, dechlorinated water. Other water chemistry parameters (pH, concentrations of DOC, calcium, magnesium and sodium) were kept relatively constant. Predictors included absorbance ratios Abs(254/365) (index of molecular weight) and Abs-octanol(254)/Abs-water(254) (index of lipophilicity), specific absorption coefficient (SAC(340); index of aromaticity), and fluorescence index (FI; index of source). In addition, the fluorescent components (humic-like, fulvic-like, tryptophan-like, and tyrosine-like) of the isolates were quantified by parallel factor analysis (PARAFAC). Up to 4-fold source-dependent differences in protection were observed amongst the different DOMs. Significant correlations in toxicity amelioration were found with Abs(254/365), Abs-octanol(254)/Abs-water(254), SAC(340), and with the humic-like fluorescent component. The relationships with FI were not significant and there were no relationships with the tryptophan-like or tyrosine-like fluorescent components at 3 mg C l(-1), whereas a negative correlation was seen with the fulvic-like component. In general, the results indicate that larger, optically dark, more lipophilic, more aromatic DOMs of terrigenous origin, with higher humic-like content, are more protective against Cu toxicity. A method for incorporating SAC(340) as a DOM quality indicator into the Biotic Ligand Model is presented; this may increase the accuracy for predicting Cu toxicity in natural waters.

Copper-induced toxicity in aqueous systems depends on its speciation and bioavailability. Natural organic matter (NOM) and reduced sulphur species can complex copper, influencing speciation and decreasing bioavailability. NOM composition in estuaries can vary, depending on inputs of terrigenous, autochthonous, or wastewater source material. At a molecular level, variability in NOM quality potentially results in different extents of copper binding. The aims of this study were to measure acute copper EC(50) values in coastal marine and estuarine waters, and identify the relationships between total dissolved copper EC(50) values and measured water chemistry parameters proportional to NOM and reduced sulphur composition. This has implications on the development of marine-specific toxicity prediction models. NOM was characterised using dissolved organic carbon (DOC) concentration and fluorescence measurements, combined with spectral resolution techniques, to quantify humic-, fulvic-, tryptophan-, and tyrosine-like fractions. Reduced sulphur was measured by the chromium-reducible sulphide (CRS) technique. Acute copper toxicity tests were performed on samples expressing extreme DOC, fluorescent terrigenous, autochthonous, and CRS concentrations. The results show significant differences in NOM quality, independent of DOC concentration. CRS is variable among the samples; concentrations ranging from 4 to 40 nM. The toxicity results suggest DOC as a very good predictive measure of copper EC(50) in estuaries (r(2)=0.87) independent of NOM quality. Furthermore, for filtered samples, CRS exists at concentrations that would be saturated with copper at measured EC(50), suggesting that while CRS might bind Cu and decrease bioavailability, it does not control copper speciation at toxicologically relevant concentrations and therefore is not a good predictive measure of copper toxicity in filtered samples.

Fluorescence characterization of dissolved organic matter (DOM) and measurements of Cr-reducible sulfide (CRS) are presented for 72 coastal marine and estuarine water samples obtained from the USA and Canada. Each sample is identified according to source: terrigenous, autochthonous, wastewater or mixed. Fluorescence data are resolved into contributions from humic, fulvic, tyrosine and tryptophan-like fluorophores. Humic and fulvic-like fluorophores correlate well with dissolved organic C (DOC) ( r 2 = 0.73 and 0.71, respectively) but tyrosine and tryptophan-like fluorophores show no correlation with DOC. Quality factors are identified by normalization of fluorescence contributions to DOC. Humic and fulvic components show no statistical differences between sources but the amino acid-like fluorescence quality factors show significant variations between source, with highest values for autochthonous sources (0.07 ± 0.01 arbitrary fluorescence units per mg of C) versus low values (0.015 ± 0.005) for terrigenous source waters. CRS concentrations are highly variable from 0.07 ± 0.01 to 7703 ± 98 nM and do no correlate with DOC except when terrigenous source waters ( n = 13) are separated out from the total sample set ( r 2 = 0.55). There is an open question in the literature; does DOC source matter in terms of protective effects towards metal toxicity? Here is shown that DOC molecular-level quality does vary and that this variation is mostly in terms of the contributions of amino acids to total fluorescence.

Deep groundwater samples from a deep borehole in the Canadian Shield, Ontario, Canada, have been analyzed by fluorometry, to determine the difference in character of the natural organic matter (NOM) with depth. This work was done to obtain a set of geochemical characteristics of deep groundwaters at the site. The fluorescence signal is a complex signature of excitation and emission of light from fluorescent molecules which are part of all natural waters. Fluorescent components have characteristic excitation/emission components, defined as a humic-like (C1), fulvic-like (C2), and protein-like (C3); these are found in various proportions in natural samples. Changes in relative fluorescence intensities of these components have been used in the past to determine the origin and/or processes of the NOM between sampling locations. In this work, six samples were taken at different depths, from ~108 to 650 m below the surface in the borehole. The fluorescence signals of the samples showed three main patterns: (1) the shallower samples (~108, 139 and 285 m) had a pattern similar to that of surface groundwaters, dominated by components C1 and C2; (2) the samples in deep groundwaters (~620 and 650 m) had a weak overall signal, dominated by component C3; finally (3) the mid-depth sample (~503 m) had a component pattern intermediate between the shallower and deeper zones. This set of data is consistent with other data for the groundwaters from this borehole, such as chlorinity, suggesting that the three sampling intervals represent three different types of groundwaters.

Aqueous natural organic matter (NOM) impacted by two contrasting human impacts was analyzed using by multiresponse fluorescence, decoupled with the resolution routine PARAFAC. The first site is Chalk River, Ontario, Canada, near a pit formerly used to dispose low-level wastes. The second site is the Grand River in Cambridge, south-central Ontario, which is impacted by urban activities and agriculture. Our analysis included raw water, plus fractions from ultrafiltration and solid-phase extraction (SPE). The fluorescence spectra of the NOM, resolved with PARAFAC, showed three common features: humic-like components, at excitation/emission wavelengths 325–350/450–475 nm, fulvic-like components at 325/380–420 nm and protein-like components, at 275/300 nm. Ultrafiltration revealed that most of the NOM comprised fine material below 5,000 Da cut-off (

Passive integrated transponder (PIT) tags are used to identify individual fishes in fish hatcheries, and to monitor habitat use, spatial movements and migratory patterns in the field. The tags are relatively inexpensive, easy to implant, and are thought to have long retention times. However, implanted tags may also invoke tissue reactions that result in their encapsulation by connective tissue. The present study examined the encapsulation of small (12 mm) and larger (23 mm) PIT tags implanted into the peritoneal cavity of brown trout (Salmo trutta). After 8 and 12 months, respectively, all 12 mm and 23 mm tags were encapsulated, but many had migrated away from the point of injection to regions that included the lumen of the intestine, the liver and heart, as well as the kidneys. The presence of PIT tags in the lumen of the intestine suggests that the gastrointestinal (GI) tract is a potential route of PIT tag expulsion by brown trout. The possibility of such adverse events may have to be considered where PIT tags are to be used in longer-term studies of this fish in aquaculture, laboratory or field settings.

Group B metals, such as Hg, Cu, Ag, Pb and Cd bind strongly to reduced inorganic and organic S(II−) ligands. These S(II−) ligands, stable in oxic waters for significant periods of time, occur at the