Additive effects of microplastics on accumulation and toxicity of cadmium in male zebrafish.

Microplastics (MPs) have emerged as contaminants of concern because of their ubiquitous presence in almost all aquatic environments. The ecological effects of MPs are complex and depend on multiple factors including their age, size and the ecological matrix. There is an urgent need for multifactorial studies to elucidate their impacts. We measured the effects of virgin and naturally aged MPs, alone, pretreated with cadmium (Cd), or in combination with ionic Cd, on the bioaccumulation of Cd, metallothionein expression, behavior, and histopathology of adult zebrafish (Danio rerio). Zebrafish were exposed to virgin or aged polyethylene MPs (0.1% MPs enriched diets, w/w) or waterborne Cd (50 µg/L) or a combination of the two for 21 days. There was an additive interaction between water-borne Cd and MPs on bioaccumulation in males but not in females. Cd accumulation increased by twofold when water-borne Cd and MPs were combined. Water-borne Cd induced significantly higher levels of metallothionein compared to MPs pre-exposed to Cd. However, Cd-treated MPs caused greater damage to the intestine and liver compared to untreated MPs suggesting that bound Cd could be released or modulate MPs toxicity. We also showed that co-exposure to water-borne Cd and MPs increased anxiety in the zebrafish, compared with water-borne Cd alone, suggesting using microplastics as a vector may increase toxicity. This study demonstrates that MPs can enhance the toxicity of Cd, but further study is needed to elucidate the mechanism.

Heavy metals levels in road dust from Muscat, Oman: relationship with traffic volumes, and ecological and health risk assessments.

Dust samples from roads classified based on traffic volumes (low, medium and high traffic) were collected from Muscat, Oman, and then analyzed for a dozen heavy metals. Their contents varied widely with mercury and iron, having the lowest and highest concentrations (0.59-0.80 and 406.10-429.00 ppm, respectively). Contrary to most metals detected, mercury and arsenic did not only exhibit increasing trends from low to high categories, but they also were significantly correlated to each other and traffic volumes, suggesting that both might originate from vehicular emissions. While the calculations revealed that the potential ecological risk index (RI) for selected metals in the dust samples was at a considerable level, the hazard index (HI) was within the safe threshold value (HI < 1). Overall, our findings imply minor prejudicial health risks to the general public nevertheless, children would be relatively more vulnerable to the impact of metals associated with dust.

Human and ecological risk assessment of heavy metals in different particle sizes of road dust in Muscat, Oman.

Heavy metal contamination of Hg, As, Cu, Cr, Zn, and Pb was investigated in three different fractions 45, 125, and 200 µm of road dust in Muscat, Oman. Dust samples were collected from three different traffic roads, viz. high, medium, and low based on traffic volume and then sieved individually before they analyzed using inductively coupled plasma optical emission spectrometry (ICP-OES). Cu has the highest level among the analyzed metals while the lowest amount was for Hg. Most of the metals in all traffic sites have higher concentration in finer fraction and the concentrations of Cu, Pb, and Zn in HT road dust decreased significantly from finer fraction (45 µm) to bigger fraction size (200 µm). The risks of analyzed heavy metals to the urban ecosystem and human health were calculated by the potential ecological risk index and human exposure model, respectively. Risk index levels of studied metals in the three fractions and roads vary from strong to very strong potential. Hg found to have the greatest contribution in risk index in the three different fractions and roads. The values of risk levels for individual metal contamination in the dust street samples from different roads and fractions were ranked in the following order: Hg > Cu > Pb > Cr > Zn. Ingestion is the main pathway of exposure to road dust particles for both children and adults, followed by dermal contact absorption. The HI for children and adults exposed to 45- and 125-µm particles were higher than exposed to 200-µm particles, which indicated that finer particles tend to have higher non-carcinogenic risk. The non-carcinogenic risks of the studied heavy metals to children and adults are within safe threshold value; however, health risks of Cr, Pb, and Cu were relatively high for children.

A global perspective on the trophic geography of sharks.

Sharks are a diverse group of mobile predators that forage across varied spatial scales and have the potential to influence food web dynamics. The ecological consequences of recent declines in shark biomass may extend across broader geographic ranges if shark taxa display common behavioural traits. By tracking the original site of photosynthetic fixation of carbon atoms that were ultimately assimilated into muscle tissues of 5,394 sharks from 114 species, we identify globally consistent biogeographic traits in trophic interactions between sharks found in different habitats. We show that populations of shelf-dwelling sharks derive a substantial proportion of their carbon from regional pelagic sources, but contain individuals that forage within additional isotopically diverse local food webs, such as those supported by terrestrial plant sources, benthic production and macrophytes. In contrast, oceanic sharks seem to use carbon derived from between 30° and 50° of latitude. Global-scale compilations of stable isotope data combined with biogeochemical modelling generate hypotheses regarding animal behaviours that can be tested with other methodological approaches.

The influence of dissolved organic matter (DOM) on sodium regulation and nitrogenous waste excretion in the zebrafish (Danio rerio).

Dissolved organic matter (DOM) is both ubiquitous and diverse in composition in natural waters, but its effects on the branchial physiology of aquatic organisms have received little attention relative to other variables (e.g. pH, hardness, salinity, alkalinity). Here, we investigated the effects of four chemically distinct DOM isolates (three natural, one commercial, ranging from autochthonous to highly allochthonous, all at ∼6 mg C l(-1)) on the physiology of gill ionoregulation and nitrogenous waste excretion in zebrafish acclimated to either circumneutral (7.0-8.0) or acidic pH (5.0). Overall, lower pH tended to increase net branchial ammonia excretion, net K(+) loss and [(3)H]PEG-4000 clearance rates (indicators of transcellular and paracellular permeability, respectively). However, unidirectional Na(+) efflux, urea excretion and drinking rates were unaffected. DOM sources tended to stimulate unidirectional Na(+) influx rate and exerted subtle effects on the concentration-dependent kinetics of Na(+) uptake, increasing maximum transport capacity. All DOM sources reduced passive Na(+) efflux rates regardless of pH, but exerted negligible effects on nitrogenous waste excretion, drinking rate, net K(+) loss or [(3)H]PEG-4000 clearance, so the mechanism of Na(+) loss reduction remains unclear. Overall, these actions appear beneficial to ionoregulatory homeostasis in zebrafish, and some may be related to physico-chemical properties of the DOM sources. They are very different from those seen in a recent parallel study on Daphnia magna using the same DOM isolates, indicating that DOM actions may be both species and DOM specific.

The effect of dissolved organic matter (DOM) on sodium transport and nitrogenous waste excretion of the freshwater cladoceran (Daphnia magna) at circumneutral and low 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).

Characterization of freshwater natural dissolved organic matter (DOM): mechanistic explanations for protective effects against metal toxicity and direct effects on organisms.

Dissolved organic matter (DOM) exerts direct and indirect influences on aquatic organisms. In order to better understand how DOM causes these effects, potentiometric titration was carried out for a wide range of autochthonous and terrigenous freshwater DOM isolates. The isolates were previously characterized by absorbance and fluorescence spectroscopy. Proton binding constants (pKa) were grouped into three classes: acidic (pKa≤5), intermediate (58.5). Generally, the proton site densities (LT) showed maximum peaks at the acidic and basic ends around pKa values of 3.5 and 10, respectively. More variably positioned peaks occurred in the intermediate pKa range. The acid-base titrations revealed the dominance of carboxylic and phenolic ligands with a trend for more autochthonous sources to have higher total LT. A summary parameter, referred to as the Proton Binding Index (PBI), was introduced to summarize chemical reactivity of DOMs based on the data of pKa and LT. Then, the already published spectroscopic data were explored and the specific absorbance coefficient at 340nm (i.e. SAC340), an index of DOM aromaticity, was found to exhibit a strong correlation with PBI. Thus, the tendencies observed in the literature that darker organic matter is more protective against metal toxicity and more effective in altering physiological processes in aquatic organisms can now be rationalized on a basis of chemical reactivity to protons.

Evaluating the ameliorative effect of natural dissolved organic matter (DOM) quality on copper toxicity to Daphnia magna: improving the BLM.

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.

Physicochemical and spectroscopic properties of natural organic matter (NOM) from various sources and implications for ameliorative effects on metal toxicity to aquatic biota.

Natural organic matter (NOM), expressed as dissolved organic carbon (DOC in mgCL(-1)), is an ubiquitous complexing agent in natural waters, and is now recognized as an important factor mitigating waterborne metal toxicity. However, the magnitude of the protective effect, judged by toxicity measures (e.g. LC50), varies substantially among different NOM sources even for similar DOC concentrations, implying a potential role of NOM physicochemical properties or quality of NOM. This review summarizes some key quality parameters for NOM samples, obtained by reverse osmosis, and by using correlation analyses, investigates their contribution to ameliorating metal toxicity towards aquatic biota. At comparable and environmentally realistic DOC levels, molecular spectroscopic characteristics (specific absorbance coefficient, SAC, and fluorescence index, FI) as well as concentrations of fluorescent fractions obtained from mathematical mixture resolution techniques (PARAFAC), explain considerable variability in the protective effects. NOM quality clearly influences the toxicity of copper (Cu) and lead (Pb). NOM quality may also influence the toxicity of silver (Ag), cadmium (Cd) and inorganic mercury (Hg), but as yet insufficient data are available to unequivocally support the latter correlations between toxicity reduction and NOM quality predictors. Cu binding capacities, protein-to-carbohydrate ratio, and lipophilicity, show insignificant correlation to the amelioration offered by NOMs, but these conclusions are based on data for Norwegian NOMs with very narrow ranges for the latter two parameters. Certainly, various NOMs alleviate metal toxicity differentially and therefore their quality measures should be considered in addition to their quantity.

Evaluating mercury biomagnification in fish from a tropical marine environment using stable isotopes (delta13C and delta15N).

Concentrations of total mercury (T-Hg) and methylmercury (MeHg) were measured in zooplankton and 13 fish species from a coastal food web of the Gulf of Oman, an arm of the Arabian Sea between Oman and Iran. Stable isotope ratios (delta13C and delta15N) also were determined to track mercury biomagnification. The average concentration of T-Hg in zooplankton was 21 +/- 8.0 ng g(-1) with MeHg accounting 10% of T-Hg. Total mercury levels in fish species ranged from 3.0 ng g(-1) (Sardinella longiceps) to 760 ng g(-1) (Rhizoprionodon acutus) with relatively lower fraction of MeHg (72%) than that found in other studies. The average trophic difference (Deltadelta13C) between zooplankton and planktivorous fish (Selar crumenopthalmus, Rastrelliger kanagurta, and S. longiceps) was higher (3.4 per thousandth) than expected, suggesting that zooplankton may not be the main diet or direct carbon source for these fish species. However, further sampling would be required to compensate for temporal changes in zooplankton and the influence of their lipid content. Trophic position inferred by delta15N and and slopes of the regression equations (log10[T-Hg] = 0.13[delta15N] - 3.57 and log10[MeHg] = 0.14[delta15N] - 3.90) as estimates of biomagnification indicate that biomagnification of T-Hg and MeHg was lower in this tropical ocean compared to what has been observed in arctic and temperate ecosystems and tropical African lakes. The calculated daily intake of methylmercury in the diet of local people through fish consumption was well below the established World Health Organization (WHO) tolerable daily intake threshold for most of the fish species except Euthynnus affinis, Epinephelus epistictus, R. acutus, and Thunnus tonggol, illustrating safe consumption of the commonly consumed fish species.

Photochemical reduction and reoxidation of aqueous mercuric chloride in the presence of ferrioxalate and air.

In this study, ferric oxalate is used to represent the photosensitive Fe(III) complexes as well as the diacid compounds which are at significant concentrations in cloud and rain droplets. Because of the common carboxylate functional group; ferric oxalate is also used as a model to represent humic substances found in natural water. UVA irradiation of aqueous acidic mercuric chloride (pH 1-4) in the presence of an excess of ferrioxalate results in partial reduction of the mercuric ion to elemental mercury. The pseudo-first-order rate constant "kobs" for the photoreduction reaction is pH-dependent as is the yield of residual Hg(II). When exposed to visible irradiation the rate is about 10 times slower and no reaction was observed in the dark. The inferred mechanism of photoreduction involves the reaction of Hg(II) with a secondary photoproduct, the strongly reducing radical anion CO2-*. In the presence of dissolved oxygen, competition for CO2-* between Hg(II) and O2 reduces the rate and efficiency of mercuric ion reduction. The O2-*/HO2 products do not reduce Hg(II). On the contrary, their disproportionation leads to the formation of H2O2 which causes a re-oxidation of Hg(0) at pH values of