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.

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.

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.

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.

The environmental consequences of nano-CuO particles have gained significant attention in recent decades. Identification of the mechanisms for soil and plant responses with respect to the chemical speciation of nano-CuO (mainly the exchangeable and reducible fractions) remains scarce. Here, we analyzed different chemical speciation of Cu and DTPA-extractable Cu over 42 days in (1) control soil without Cu addition; (2) soil treated with nano-CuO particles; and (3) soil treated with CuSO₄ solution. The applied dose was 500 mg Cu kg⁻¹ and maize was grown in these soils. Plant growth was inhibited, but the inhibition by nano-CuO was slightly weaker compared to CuSO₄. Cu accumulations were similar in the roots for CuSO₄ and nano-CuO treatments, but significantly higher in the shoots for CuSO₄ treatment. This indicates that Cu from nano-CuO-treated soils mainly accumulated in roots but rarely transferred to shoots. Enzyme activities on the rhizoplane visualized by zymography were strongly depressed by CuSO₄ but slightly inhibited by nano-CuO. Microbial community diversity measured by 16S rRNA was the lowest in CuSO₄-treated soils among three treatments. These results were explained by the following mechanisms: (1) Gradual increases of DTPA-extractable and exchangeable Cu were found in nano-CuO-treated soil, and the final concentrations at day 42 were only half of those in CuSO₄-treated soil; (2) Enzyme activities on the rhizoplane were positively related to soil pH and negatively correlated with DTPA-extractable and exchangeable Cu; (3) Even though reducible Cu in nano-CuO-treated soils was 1.3 times higher than in CuSO₄-treated soils, indicating stronger nano-accrued oxidative stress in nano-CuO-treated soils, the toxicity induced by nano-CuO particles was still weaker than CuSO₄. Nevertheless, the toxicity of Cu particles to plants and microbes mainly depends on the gradually-released bioavailable Cu. This demonstrates the greater importance of bioavailable Cu concentrations for toxicity modulation rather than the scale of Cu particles.

Bulk Cu compounds such as Cu(OH)₂ are extensively used as pesticides in agriculture. Recent investigations suggest that Cu-based nanomaterials can replace bulk materials reducing the environmental impacts of Cu. In this study, stress responses of alfalfa (Medicago sativa L.) seedlings to Cu(OH)₂ nanoparticle or compounds were evaluated. Seeds were immersed in suspension/solutions of a Cu(OH)₂ nanoform, bulk Cu(OH)₂, CuSO₄, and Cu(NO₃)₂ at 25 and 75 mg/L. Six days later, the germination, seedling growth, and the physiological and biochemical responses of sprouts were evaluated. All Cu treatments significantly reduced root elongation (average = 63%). The ionic compounds at 25 and 75 mg/L caused a reduction in all elements analyzed (Ca, K, Mg, P, Zn, and Mn), excepting for S, Fe and Mo. The bulk-Cu(OH)₂ treatment reduced K (48%) and P (52%) at 75 mg/L, but increased Zn at 25 (18%) and 75 (21%) mg/L. The nano-Cu(OH)₂ reduced K (46%) and P (48%) at 75 mg/L, and also P (37%) at 25 mg/L, compared with control. Confocal microscopy images showed that all Cu compounds, at 75 mg/L, significantly reduced nitric oxide, concurring with the reduction in root growth. Nano Cu(OH)₂ at 25 mg/L upregulated the expression of the Cu/Zn superoxide dismutase gene (1.92-fold), while ionic treatments at 75 mg/L upregulated (∼10-fold) metallothionein (MT) transcripts. Results demonstrated that nano and bulk Cu(OH)₂ compounds caused less physiological impairments in comparison to the ionic ones in alfalfa seedlings.

Environmental reservoirs of antibiotic resistant bacteria are poorly understood. Understanding how the environment selects for resistance traits in the absence of antibiotics is critical in developing strategies to mitigate this growing menace. Indirect or co-selection of resistance by environmental pollution has been shown to increase antibiotic resistance. However no attention has been given to the effects of low-level ionizing radiation or the interactions between radiation and heavy metals on the maintenance or selection for antibiotic resistance (AR) traits. Here we explore the effect of radiation and copper on antibiotic resistance. Bacteria were collected from biofilms in two ponds – one impacted by low-level radiocesium and the other an abandoned farm pond. Through laboratory controlled experiments we examined the effects of increasing concentrations of copper on the incidence of antibiotic resistance. Differences were detected in the resistance profiles of the controls from each pond. Low levels (0.01 mM) of copper sulfate increased resistance but 0.5 mM concentrations of copper sulfate depressed the AR response in both ponds. A similar pattern was observed for levels of multiple antibiotic resistance per isolate. The first principal component response of isolate exposure to multiple antibiotics showed significant differences among the six isolate treatment combinations. These differences were clearly visualized through a discriminant function analysis, which showed distinct antibiotic resistance response patterns based on the six treatment groups.