Mosses are frequently used to monitor atmospheric metal contamination but few studies on metal adsorption under controlled conditions are available. Here, the accumulation of the heavy metals copper and zinc was studied in the acrocarp moss Atrichum undulatum. An in vitro culture of A. undulatum was established and the same line, size and equally old remets were exposed to six different treatments representing various metal exposure times and washing scenarios as rain simulation. The metal treatments were done in copper and zinc salts (Cu-acetate, CuSO4, ZnSO4 and ZnCl2, respectively). Energy-Dispersive X-ray microanalysis (EDX) was employed to detect bound heavy metals on the moss plantlets. Element distribution in stems and leaves was measured separately. The aqueous solution of metal salts facilitated an adsorption of both elements in the moss tissue as compared to solid medium. Furthermore, A. undulatum can tolerate pollution of zinc and copper in a distinctive extent; our data point towards a higher zinc tolerance whereas copper is rather harmful. However, semi-quantitatively, less zinc was detected within the moss tissue compared to copper. Interestingly, a strong positive correlation between the accumulation of copper/zinc and iron, and a strong negative correlation between copper/zinc and magnesium, respectively, was documented.

Cu nanoparticles (CuNPs) have been widely used in numerous products, and may become a potential threat to marine organisms, but their behavior in the marine environments and potential toxicity to marine organisms remain little known. In the present study, we investigated the behavior of CuNPs in seawater, as well as the toxicity and bioaccumulation of CuNPs and copper sulfate (CuSO4) in barnacle larvae (Balanus amphitrite), a dominant fouling invertebrate in marine environment. CuNPs tended to aggregate in natural seawater and released Cu ion rapidly into seawater. The aggregation and release were especially higher at a lower concentration of CuNPs, e.g., 94–96% of CuNPs were released as Cu ions at 20 μg/L after 24 h. The larger size of CuNPs (40 nm) tended to display a higher solubility than the 20 nm CuNPs did. Humic acids enhanced the aggregation and inhibited the dissolution of CuNPs, and had a protective effect on the survival of nauplii II at higher Cu concentrations (100–200 μg/L). Comparison of the lethal concentrations showed that CuNPs were generally less toxic to the two stages of barnacle larvae (nauplii II and VI) than the Cu ions. The calculated 48-h LC50 values for nauplii II were 189.5 μg/L, 123.2 μg/L, and 89.8 μg/L for 20 nm CuNPs, 40 nm CuNPs, and CuSO4, respectively. However, the lethal concentrations of Cu bioaccumulation in the barnacle larvae were comparable between CuNPs and Cu ions when expressed by the actual tissue Cu bioaccumulation. Barnacle larval settlement decreased with an increase of Cu concentrations of both CuNPs and CuSO4, and was significantly inhibited at 100 μg/L CuSO4 and 150 μg/L CuNPs. Our results indicated that the toxicity of CuNPs could not be solely explained by the released Cu ions, and both CuNPs and the released Cu ion contributed to their toxicity and bioaccumulation in barnacle larvae.

This paper evaluates the UV photodegradation of 17β-estradiol (E2) on silica gel and in natural soil with different soil components. Silica gel was chosen as a stable and pure support to simulate the photochemical behavior of E2 on the surface of natural soil. Ultraviolet light, rather than visible light, was confirmed to play a decisive role in the photodegradation of E2 on silica gel. The effect of three soil components, including humic acid (HA), inorganic salts, and relative humidity (RH), on the photochemical behavior of E2 on silica gel or soil under UV irradiation was then evaluated. Two HA concentrations (10 and 20 mg g⁻¹) and three salts (ferric sulfate, copper sulfate and sodium carbonate) were observed to obviously inhibit the degradation of E2 on silica gel. Interestingly, nitrate was found to obviously improve the removal efficiency of E2. Both too-dry and too-wet conditions obviously reduced the removal rate of E2, and the optimum relative humidity (RH) value was found to be approximately about 35% (30 °C). Furthermore, twenty intermediate products and two major pathways were proposed to describe the transformation processes of E2 treated by UV irradiation, among which oligomers were found to be the major intermediate products before complete mineralization. The efficient UV removal of E2 on silica gel and natural soil suggested a feasible strategy to remediate E2 contaminated soil.

Copper nanoparticles (nCu) are widely used in industry and in daily life, due to their unique physical, chemical, and biological properties. Few studies have focused on nCu phytotoxicity, especially with regard to toxicity mechanisms in crop plants. The present study examined the effect of 15.6 μM nCu exposure on the root morphology, physiology, and gene transcription levels of wheat (Triticum aestivum L.), a major crop cultivated worldwide. The results obtained were compared with the effects of exposing wheat to an equivalent molar concentration of ionic Cu (Cu²⁺ released from CuSO₄) and to control plants. The relative growth rate of roots decreased to approximately 60% and the formation of lateral roots was stimulated under nCu exposure, possibly due to the enhancement of nitrogen uptake and accumulation of auxin in lateral roots. The expression of four of the genes involved in the positive regulation of cell proliferation and negative regulation of programmed cell death decreased to 50% in the Cu²⁺ treatment compared to that of the control, while only one gene was down-regulated to about half of the control in nCu treatment. This explained the decreased root cell proliferation and higher extent of induced cell death in Cu²⁺- than in nCu-exposed plants. The increased methane dicarboxylic aldehyde accumulation (2.17-fold increase compared with the control) and decreased antioxidant enzyme activities (more than 50% decrease compared with the control) observed in the Cu²⁺ treatment in relation to the nCu treatment indicated higher oxidative stress in Cu²⁺- than in nCu-exposed plants. Antioxidant (e.g., proline) synthesis was pronouncedly induced by nCu to scavenge excess reactive oxygen species, alleviating phytotoxicity to wheat exposed to this form of Cu. Overall, oxidative stress and root growth inhibition were the main causes of nCu toxicity.

Pyrethroid-resistant Hyalella azteca with voltage-gated sodium channel mutations have been identified at multiple locations throughout California. In December 2013, H. azteca were collected from Mosher Slough in Stockton, CA, USA, a site with reported pyrethroid (primarily bifenthrin and cyfluthrin) sediment concentrations approximately twice the 10-d LC50 for laboratory-cultured H. azteca. These H. azteca were shipped to Southern Illinois University Carbondale and have been maintained in pyrethroid-free culture since collection. Even after 22 months in culture, resistant animals had approximately 53 times higher tolerance to permethrin than non-resistant laboratory-cultured H. azteca. Resistant animals held in culture also lacked the wild-type allele at the L925 locus, and had non-synonymous substitutions that resulted in either a leucine-isoleucine or leucine-valine substitution. Additionally, animals collected from the same site nearly three years later were again resistant to the pyrethroid permethrin. When resistant animals were compared to non-resistant animals, they showed lower reproductive capacity, lower upper thermal tolerance, and the data suggested greater sensitivity to, 4, 4′-dichlorodiphenyltrichloroethane (DDT), copper (II) sulfate, and sodium chloride. Further testing of the greater heat and sodium chloride sensitivity of the resistant animals showed these effects to be unrelated to clade association. Fitness costs associated with resistance to pyrethroids are well documented in pest species (including mosquitoes, peach-potato aphids, and codling moths) and we believe that H. azteca collected from Mosher Slough also have fitness costs associated with the developed resistance.

Se laden freshwater algae that enter the Salton Sea with river water pose ecorisks to wildlife in the lake by transferring selenium (Se) to higher trophic levels. The aim of this study was to investigate impacts of Se on Microcystis aeruginosa, widely distributed in freshwater bodies, and its relationship with toxicity, such as microcystins and Se residues. When supplied with selenite, the 96 h-IC50 was calculated 2.60 mg Se/L. However, these inhibitory effects did not extend to microcystin production, and the extracellular fraction significantly increased with selenite as well as sulfate. As M. aeruginosa assimilated selenite very efficiently, 97% of the removed Se was through accumulation, compared to 3% via volatilization, raising a concern about ecotoxicity caused by the remaining Se in the algae. The XAS analysis suggests the dominant Se species accumulated in the algal cells was elemental Se (81%), which is relatively nonbioavailable to aquatic organisms. We further investigated the potential fate of Se carried into the Salton Sea by M. aeruginosa with river water. Under hypersalinity stress, the biomass Se and intracellular microcystins were released and reduced by 47% and 74%, respectively, resulting in the increasing levels of Se and microcystins in the water column. CuSO4 was then applied as an algaecide to prevent M. aeruginosa from entering the lake. The results indicate a similar response to that under hypersalinity stress: the volatilization process was blocked and the Se and microcystins were released from the damaged algal cells in the presence of CuSO4, further raising toxicity levels by 8% and 60%, respectively, in the water column within 24 h. Overall, the coexistence of selenite and M. aeruginosa in river waters might negatively impact aquatic ecosystems of the Salton Sea and further research is required on how to harvest Se from M. aeruginosa to protect local wildlife.

The feasibility of assessing copper accumulation in agricultural soils using avoidance tests with a Canadian strain of Folsomia candida was investigated under laboratory conditions. The avoidance response to nominal copper sulfate concentrations of 0, 200, 800, 1600 and 3200 mg kg⁻¹ in OECD soil was inconsistent between trials with the standard plastic cup or a modified Petri dish method requiring less soil. However, combined results from three Petri dish trials decreased variability and provided a 75% avoidance level, close to the 80% criterion proposed for avoidance tests. A Copper avoidance EC₅₀ₛ of 18 mg kg⁻¹was obtained using the Petri dish method whether tests were conducted with or without light. While Petri dish tests have potential as a cheap tool to distinguish metal contaminated soils from uncontaminated soils they would be unsuitable for tracking or quantifying changes in metal concentrations. throughout remediation. Advantages and limitations of the method have been presented.

Gradual contamination of agricultural land with copper (Cu), due to the indiscriminate uses of fungicides and pesticides, and the discharge of industrial waste to the environment, poses a high threat for soil degradation and consequently food crop production. In this study, we combined morphological, physiological and biochemical assays to investigate the mechanisms underlying acetate-mediated Cu toxicity tolerance in lentil. Results demonstrated that high dose of Cu (3.0 mM CuSO₄. 5H₂O) reduced seedling growth and chlorophyll content, while augmenting Cu contents in both roots and shoots, and increasing oxidative damage in lentil plants through disruption of the antioxidant defense. Principle component analysis clearly indicated that Cu accumulation and increased oxidative damage were the key factors for Cu toxicity in lentil seedlings. However, acetate pretreatment reduced Cu accumulation in roots and shoots, increased proline content and improved the responses of antioxidant defense (e.g. increased catalase and glutathione-S-transferase activities, and improved action of glutathione-ascorbate metabolic pathway). As a result, excess Cu-induced oxidative damage was reduced, and seedling growth was improved under Cu stress conditions, indicating the role of acetate in alleviating Cu toxicity in lentil seedlings. Taken together, exogenous acetate application reduced Cu accumulation in lentil roots and shoots and mitigated oxidative damage by activating the antioxidant defense, which were the major determinants for alleviating Cu toxicity in lentil seedlings. Our findings provide mechanistic insights into the protective roles of acetate in mitigating Cu toxicity in lentil, and suggest that application of acetate could be a novel and economical strategy for the management of heavy metal toxicity and accumulation in crops.

In aquatic environments, organisms such as freshwater mussels are likely exposed to complex contaminant mixtures related to industrial, agricultural, and urban activities. With growing interest in understanding the risk that chemical mixtures pose to mussels, this investigation focused on the effects of various waterborne contaminants (ammonia, chloride, copper, and potassium) and selected binary mixtures of these chemicals following a fixed-ratio design to Villosa iris glochidia and juvenile Lampsilis fasciola. In individual exposures, 48-h EC50 values were determined for V. iris glochidia exposed to ammonia chloride (7.4 [95% confidence interval (CI) 6.6–8.2] mg N/L), ammonia sulfate (8.4 [7.6–9.1] mg N/L), copper sulfate (14.2 [12.9–15.4] μg Cu2+/L), potassium chloride (12.8 [11.9–13.7] mg K+/L), potassium sulfate (10.1 [8.9–11.2] mg K+/L), and sodium chloride (480.5 [435.5–525.5] mg Cl−/L). The 7-d LC50 values for juvenile L. fasciola were determined for potassium sulfate (45.0 [18.8–71.2] mg K+/L), and sodium chloride (1738.2 [1418.6–2057.8] mg Cl−/L). In Ontario these waterborne contaminants have been reported to co-occur, with concentrations exceeding the EC10 for both life stages at some locations. Data from binary mixture exposures for V. iris glochidia (chloride-ammonia, chloride-copper, and copper-ammonia) and juvenile L. fasciola (chloride-potassium) were analyzed using a regression-based, dose-response mixture analysis modeling framework. Results from the mixture analysis were used to determine if an additive model for mixture toxicity [concentration addition (CA) or independent action (IA)] best described the toxicity of each mixture and if deviation towards dose-ratio (DR) or dose-level (DL) synergism/antagonism (S/A) occurred. For all glochidia binary mixture exposures, CA was the best fit model with DL deviation reported for the chloride-copper mixture and DR deviation reported for the copper-ammonia mixture. Using the model deviation ratio (MDR), the observed toxicity in all three glochidia mixture exposures were adequately described by both CA (mean = 0.71) and IA (mean = 0.97) whereas the juvenile mixture exposure was only adequately described by CA (mean = 0.64; IA mean = 0.05).

Toxicity of Cu and Cu-based nanoparticles (NPs) to aquatic biota is usually mitigated in natural freshwater compared to organics-free artificial freshwater. The main aim of this study was to evaluate whether mitigated toxicity is accompanied by lower total copper body burden in the freshwater crustacean Daphnia magna and whether CuO NPs are more hazardous in this aspect than soluble Cu salts.Total copper body burden in different media (OECD202 artificial freshwater and two natural freshwaters) was measured by a relatively novel technique - total reflection X-ray fluorescence (TXRF) spectroscopy - which proved suitable for the analysis of individual juvenile daphnids. Mean copper body burden was 2.8–42 times higher in daphnids exposed to CuO NPs (0.05 mg Cu/L and 1 mg Cu/L) than in daphnids exposed to equal or equitoxic concentrations (0.025 mg Cu/L and 0.05 mg Cu/L) of CuSO4. Using natural freshwater instead of artificial one resulted in increased copper burden after exposure to CuO NPs but not after exposure to Cu salt. After 24 h post-exposure depuration in the presence of algae Raphidocelis subcapitata, total copper body burden in daphnids exposed to CuO NPs sharply decreased while in daphnids exposed to Cu salt it did not. Despite the CuO NP toxicity mitigating effect of natural freshwater, total copper body burden of aquatic crustaceans in natural waterbodies may be greater than could be predicted based on the results obtained using artificial freshwater as the test medium.