Effects of various physicochemical characteristics on the toxicities of ZnO and TiO nanoparticles toward human lung epithelial cells

Although novel nanomaterials are being produced and applied in our daily lives at a rapid pace, related health and environmental toxicity assessments are lagging behind. Recent reports have concluded that the physicochemical properties of nanoparticles (NPs) have a crucial influence on their toxicities and should be evaluated during risk assessments. Nevertheless, several controversies exist regarding the biological effects of NP size and surface area. In addition, relatively few reports describe the extents to which the physicochemical properties of NPs influence their toxicity. In this study, we used six self-synthesized and two commercial ZnO and TiO₂ nanomaterials to evaluate the effects of the major physicochemical properties of NPs (size, shape, surface area, phase, and composition) on human lung epithelium cells (A549). We characterized these NPs using transmission electron microscopy, X-ray diffraction, the Brunauer-Emmett-Teller method, and dynamic laser scattering. From methyl thiazolyl tetrazolium (MTT) and Interleukin 8 (IL-8) assays of both rod- and sphere-like ZnO NPs, we found that smaller NPs had greater toxicity than larger ones—a finding that differs from those of previous studies. Furthermore, at a fixed NP size and surface area, we found that the nanorod ZnO particles were more toxic than the corresponding spherical ones, suggesting that both the size and shape of ZnO NPs influence their cytotoxicity. In terms of the effect of the surface area, we found that the contact area between a single NP and a single cell was more important than the total specific surface area of the NP. All of the TiO₂ NP samples exhibited cytotoxicities lower than those of the ZnO NP samples; among the TiO₂ NPs, the cytotoxicity increased in the following order: amorphous > anatase > anatase/rutile; thus, the phase of the NPs can also play an important role under size-, surface area-, and shape-controlled conditions.     

Synergistic toxic effect of nano-TiO and As(V) on Ceriodaphnia dubia

Due to the active development and application of nanotechnology, engineered nanomaterials (ENMs) are becoming a new class of environmental pollutants that may significantly impact the environment and human health. While many toxicity investigations have been conducted, there is little information about the synergistic effect of ENMs and other toxic compounds in the environment. In order to extend this knowledge, the combined effect of TiO₂ nanoparticles (n-TiO₂) and As(V) were investigated. High concentrations of As(V) can accumulate on the n-TiO₂ surface. Cultured Ceriodaphnia dubia (C. dubia) species were used to examine the synergistic toxic effect through exposure to 1) n-TiO₂ suspensions, 2) As(V) solutions, and 3) mixtures of n-TiO₂ and As(V) suspensions. Results showed that n-TiO₂ alone was not toxic when the concentration was less than 400 mg/L and that the 24-hour median lethal concentration (LC₅₀) of As(V) alone was 3.68 ± 0.22 mg/L. However, in the presence of low concentrations of n-TiO₂, the toxicity of As(V) increased significantly. At the same initial As(V) concentration, the toxicity of n-TiO₂ first increased, reached a maximum, and then decreased with an increase in n-TiO₂ concentration. Hydrodynamic size and sorption capacity were most important parameters for toxicity.     

Analysis of environmental endocrine disrupting chemicals using the E-screen method and stir bar sorptive extraction in wastewater treatment plant effluents

Endocrine disrupting chemicals (EDCs) have become a major issue in the field of environmental science due to their ability to interfere with the endocrine system. Recent studies show that surface water is contaminated with EDCs, many released from wastewater treatment plants (WWTP). This pilot study used biological (E-screen assay) and chemical (stir bar sorptive extraction-GC-MS) analyses to quantify estrogenic activity in effluent water samples from a municipal WWTP and in water samples of the recipient river, upstream and downstream of the plant.The E-screen assay was performed on samples after solid phase extraction (SPE) to determine total estrogenic activity; the presence of estrogenic substances can be evaluated by measuring the 17-β-estradiol equivalency quantity (EEQ). Untreated samples were also assayed with an acute toxicity test (Vibrio fischeri) to study the correlation between toxicity and estrogenic disruption activity.Mean EEQs were 4.7 ng/L (± 2.7 ng/L) upstream and 4.4 ng/L (± 3.7 ng/L) downstream of the plant, and 11.1 ng/L (± 11.7 ng/L) in the effluent. In general the WWTP effluent had little impact on estrogenicity nor on the concentration of EDCs in the river water. The samples upstream and downstream of the plant were non-toxic or weakly toxic (0 < TU < 0.9) while the effluent was weakly toxic or toxic (0.4 < TU < 7.6). Toxicity and estrogenic activity were not correlated.At most sites, industrial mimics, such as the alkylphenols and phthalates, were present in higher concentrations than natural hormones. Although the concentrations of the detected xenoestrogens were generally higher than those of the steroids, they accounted for only a small fraction of the EEQ because of their low estrogenic potency. The EEQs resulting from the E-screen assay and those calculated from the results of chemical analyses using estradiol equivalency factors were comparable for all samples and closely correlated.     

Toxicity of nanoparticles of CuO, ZnO and TiO2 to microalgae Pseudokirchneriella subcapitata

Toxicities of ZnO, TiO₂ and CuO nanoparticles to Pseudokirchneriella subcapitata were determined using OECD 201 algal growth inhibition test taking in account potential shading of light. The results showed that the shading effect by nanoparticles was negligible. ZnO nanoparticles were most toxic followed by nano CuO and nano TiO₂. The toxicities of bulk and nano ZnO particles were both similar to that of ZnSO₄ (72 h EC50 ~ 0.04 mg Zn/l). Thus, in this low concentration range the toxicity was attributed solely to solubilized Zn²⁺ ions. Bulk TiO₂ (EC50 = 35.9 mg Ti/l) and bulk CuO (EC50 = 11.55 mg Cu/l) were less toxic than their nano formulations (EC50 = 5.83 mg Ti/l and 0.71 mg Cu/l). NOEC (no-observed-effect-concentrations) that may be used for risk assessment purposes for bulk and nano ZnO did not differ (~ 0.02 mg Zn/l). NOEC for nano CuO was 0.42 mg Cu/l and for bulk CuO 8.03 mg Cu/l. For nano TiO₂ the NOEC was 0.98 mg Ti/l and for bulk TiO₂ 10.1 mg Ti/l. Nano TiO₂ formed characteristic aggregates entrapping algal cells that may contribute to the toxic effect of nano TiO₂ to algae. At 72 h EC50 values of nano CuO and CuO, 25% of copper from nano CuO was bioavailable and only 0.18% of copper from bulk CuO. Thus, according to recombinant bacterial and yeast Cu-sensors, copper from nano CuO was 141-fold more bioavailable than from bulk CuO. Also, toxic effects of Cu oxides to algae were due to bioavailable copper ions.To our knowledge, this is one of the first systematic studies on effects of metal oxide nanoparticles on algal growth and the first describing toxic effects of nano CuO towards algae.     

Effects of nano-scale TiO2, ZnO and their bulk counterparts on zebrafish: acute toxicity, oxidative stress and oxidative damage

The acute toxicity and oxidative effects of nano-scale titanium dioxide, zinc oxide and their bulk counterparts in zebrafish were studied. It was found that although the size distribution of nanoparticles (NPs) was similar to that of the bulk particles in suspension, the acute toxicity of the TiO₂ NPs (96-h LC₅₀ of 124.5 mg/L) to zebrafish was greater than that of the bulk TiO₂, which was essentially non-toxic. The acute toxicities observed for ZnO NPs, a bulk ZnO suspension, and a Zn²⁺ solution were quite similar to each other (96-h LC₅₀ of 4.92, 3.31 and 8.06 mg/L, respectively). In order to explore the underlying toxicity mechanisms of NPs, ·OH radicals generated by NPs in suspensions and five biomarkers of oxidative effects, i.e. superoxide dismutase, catalase activities, malondialdehyde, reduced glutathione and protein carbonyl were investigated. Results showed that after the illumination for 96 h, the quantities of ·OH in the NP suspensions were much higher than ones in the bulk particles suspensions. The malondialdehyde content of zebrafish gills exposed to either illumination or dark were 217.2% and 174.3% of controls, respectively. This discrepancy indicates the occurrence of lipid peroxidation which is partly due to the generation of ·OH. In contrast, exposure to 5 mg/L ZnO NPs and bulk ZnO suspension induced oxidative stress in the gills without oxidative damage. Oxidative effects were more severe in the livers, where the protein carbonyl content, in the light and dark groups exposed to 50 mg/L TiO₂ NPs, was 178.1% and 139.7% of controls, respectively. The malondialdehyde levels in the liver of fish exposed to 5 mg/L ZnO NPs and bulk ZnO were elevated (204.2% and 286.9% of controls, respectively). Additionally, gut tissues exhibited oxidative effects after exposure to NP suspensions. These results highlight the importance of a systematic assessment of metal oxide NP toxicity mechanisms.     

Exploration of CeO₂ nanoparticles as a chemi-sensor and photo-catalyst for environmental applications

CeO₂ nanoparticles were synthesized hydrothermally and utilized as redox mediator for the fabrication of efficient ethanol chemi-sensor. The developed chemi-sensor showed an excellent performance for electrocatalytic oxidization of ethanol by exhibiting higher sensitivity (0.92 μA?cm^− 2?mM^− 1) and lower limit of detection (0.124 ± 0.010 mM) with the linear dynamic range of 0.17 mM-0.17 M. CeO₂ nanoparticles have been characterized by field emission scanning electron microscopy (FESEM), Energy dispersive spectroscopy (EDS), X-ray powder diffraction (XRD), Raman spectrum, Fourier transform infrared spectroscopy (FTIR), and UV-visible absorption spectrum which revealed that the synthesized CeO₂ is an aggregated form of optically active spherical nanoparticles with the range of 15-36 nm (average size of ~ 25 ±10 nm) and possessing well crystalline cubic phase. Additionally, CeO₂ performed well as a photo-catalyst by degrading amido black and acridine orange.     

Bacterial response to a shock load of nanosilver in an activated sludge treatment system

The growing release of nanosilver into sewage systems has increased the concerns on the potential adverse impacts of silver nanoparticles (AgNPs) in wastewater treatment plants. The inhibitory effects of nanosilver on wastewater treatment and the response of activated sludge bacteria to the shock loading of AgNPs were evaluated in a Modified Ludzack-Ettinger (MLE) activated sludge treatment system. Before shock-loading experiments, batch extant respirometric assays determined that at 1 mg/L of total Ag, nitrification inhibitions by AgNPs (average size = 1-29 nm) and Ag⁺ ions were 41.4% and 13.5%, respectively, indicating that nanosilver was more toxic to nitrifying bacteria in activated sludge than silver ions. After a 12-h period of nanosilver shock loading to reach a final peak silver concentration of 0.75 mg/L in the MLE system, the total silver concentration in the mixed liquor decreased exponentially. A continuous flow-through model predicted that the silver in the activated sludge system would be washed out 25 days after the shock loading. Meanwhile, a prolonged period of nitrification inhibition (>1 month, the highest degree of inhibition = 46.5%) and increase of ammonia/nitrite concentration in wastewater effluent were observed. However, nanosilver exposure did not affect the growth of heterotrophs responsible for organic matter removal. Microbial community structure analysis indicated that the ammonium-oxidizing bacteria and nitrite-oxidizing bacteria, Nitrospira, had experienced population decrease while Nitrobacter was washed out after the shock loading.     

Physical, mechanical and thermal properties of concrete in different curing media containing ZnO2 nanoparticles

In the present work, the effect of curing medium on microstructure together with physical, mechanical and thermal properties of concrete containing ZnO₂ nanoparticles have been investigated. Portland cement was partially replaced by ZnO₂ nanoparticles with the average particle size of 15 nm and the specimens were cured in water and saturated limewater for specific ages. The results indicate that ZnO₂ nanoparticles up to maximum of 2.0% produces concrete with improved compressive strength and setting time when the specimens cured in saturated limewater. The optimum level of replacement for cured specimens in water is 1.0 wt%. Although the limewater reduces the strength of concrete without nanoparticles when it is compared with the specimens cured in water, curing the specimens bearing nanoparticles in saturated limewater results in more strengthening gel formation around ZnO₂ nanoparticles causes more rapid setting time together with high strength. Accelerated peak appearance in conduction calorimetry tests, more weight loss in thermogravimetric analysis and more rapid appearance of peaks related to hydrated products in X-ray diffraction results, all indicate that ZnO₂ nanoparticles could improve mechanical and physical properties of the specimens.     

Al2O3 nanoparticles in concrete and different curing media

In the present study, the effect of limewater on strength and percentage of water absorption of Al₂O₃ nanoparticles blended concrete has been investigated. Portland cement was partially replaced by Al₂O₃ nanoparticles with the average particle size of 15 nm with different amount and the specimens were cured in water and saturated limewater for specific ages. Utilizing up to 2.0 wt% Al₂O₃ nanoparticles could produce concrete with improved strength and water permeability when the specimens cured in saturated limewater while this content is 1.0 wt% for the specimens cured in tap water. The high action of fine nanoparticles substantially increases the quantity of C-S-H gel. Although the limewater reduces the strength of concrete without nanoparticles when compared with that cured in water, curing the specimens in saturated limewater results in more strengthening gel formation around Al₂O₃ nanoparticles and causes improved permeability together with high strength. In addition, Al₂O₃ nanoparticles are able to act as nanofillers and recover the pore structure of the specimens by decreasing harmful pores. Accelerated peak appearance in conduction calorimetry tests, more weight loss in thermogravimetric analysis and more rapid appearance of peaks related to hydrated products in X-ray diffraction results, all indicate that Al₂O₃ nanoparticles could improve mechanical and physical properties of the specimens.     

Dechlorination of trichloroethylene by Ni/Fe nanoparticles immobilized in PEG/PVDF and PEG/nylon 66 membranes

The highly reactive bimetallic Fe/Ni nanoparticles immobilized in nylon 66 and PVDF membranes were synthesized and characterized for dechlorination of trichloroethylene (TCE) under anoxic conditions. Scanning electron microscopy (SEM) images and electron probe microanalysis (EPMA) elemental maps showed that the distribution of Fe in nylon 66 membrane was uniform and the intensity of Ni layer was higher than that in PVDF membrane. The particle sizes of bimetallic Fe/Ni in PVDF and nylon 66 membranes were 81 ± 12 and 55 ± 14 nm with the Ni layers of 12 ± 3 and 15 ± 2 nm, respectively. Low agglomeration of immobilized Fe/Ni nanoparticles in nylon 66 membrane was observed, presumably attributed to the more multifunctional chelating groups in membrane. A rapid hydrodechlorination of TCE with ethane as the main end product was observed by the immobilized Fe/Ni nanoparticles. The pseudo-first-order rate constants for TCE dechlorination were 6.44 ± 0.32 and 1.66 ± 0.08 h⁻¹ for nylon 66 and PVDF membranes, respectively. In addition, the efficiency and rate of TCE dechlorination increased upon increasing the mass loading of Ni, ranging between 2.5 and 20 wt%, and then decreased when further increased the Ni loading to 25 wt%. In addition, the stability and longevity of the immobilized Fe/Ni nanoparticles was evaluated by repeatedly injecting TCE into the solutions. A rapid and complete dechlorination of TCE by trace amounts of Fe/Ni nanoparticles was observed after 16 cycles of injection within 10 days, indicating that the immobilization of Fe/Ni nanoparticles in the hydrophilic nylon 66 membrane can retain the longevity and high reactivity of nanoparticles towards TCE dechlorination.     

The effect of humic acids on the cytotoxicity of silver nanoparticles to a natural aquatic bacterial assemblage

The effect of a terrestrial humic acid (HA) and a river HA on the cytotoxicity of silver nanoparticles (AgNPs) to natural aquatic bacterial assemblages (0 μM, 2.5 μM and 5 μM) was measured with spread plate counting. The effect of HA (20 and 40 ppm) on the cytotoxicity of AgNPs ranging in size between 15 and 25 nm was tested in the presence and in the absence of natural sunlight. The experiment was a full factorial, completely randomized design and the results were analyzed using the General Linear Model in SAS. LSMEANS was used to separate the means or combinations of means. Significant main effects of all independent variables, plus interaction effects in all cases except HA/LI and HA/AgNPs/LI were observed. The toxicity of AgNPs to natural aquatic bacterial assemblages appears to be concentration dependent for concentrations between 0 μM and 5 μM. The data indicate that the light exposure inhibited viability more than the darkness exposure. The HA treatment groups in the presence of light showed greater reduced viability count compared to darkness exposure groups. The inhibition of bacterial viability counts by AgNPs exposure was less in the light treatment groups containing a terrestrial HA compared to that with a river HA. Difference in the extent of reactive oxygen species formation and adsorption/binding of AgNPs was speculated to account for the observed phenomenon.     

Degradation models and ecotoxicity in marine waters of two antifouling compounds: Sodium hypochlorite and an alkylamine surfactant

Industrial wastes have a substantial impact on coastal environments. Therefore, to evaluate the impact of cooling water discharges from coastal power plants, we studied the kinetics of the degradative processes and the ecotoxicity of two antifouling products: (1) a classic antifouling product; sodium hypochlorite (NaClO) and (2) an alternative one; aliphatic amines (commercial under the registered trade mark Mexel^®432). To assess the persistence of both compounds the decay of sodium hypochlorite and the primary biodegradation rate of Mexel^®432 were determined in natural seawater at 20 °C. The results indicated a more rapid decay of NaClO than Mexel^®432. The degradation behavior of both chemicals was described following a logistic model, which permitted calculating kinetic parameters such as t₅₀ or t₉₀. The t₅₀ was 1 h and 2 d for NaClO and Mexel^®432, respectively. To evaluate the potential risks of the aforementioned treatments to marine organisms, the acute toxicity of both antifouling products was studied on the microalgae Isochrysis galbana and Dunaliella salina, and on the invertebrate Brachionus plicatilis, using growth inhibition and death tests as toxic response, respectively. For I. galbana, the 96-h EC₅₀ values were 2.91 ± 0.15 mg/L of NaClO and 4.55 ± 0.11 mg/L of Mexel^®432. D. salina showed values of 96-h EC₅₀ of 1.73 ± 0.16 mg/L of NaClO and 7.21 ± 0.1 mg/L of Mexel^®432. Brachionus plicatilis showed a 24-h LC₅₀ of 1.23 ± 0.1 mg/L of NaClO and 3.62 ± 0.37 mg/L of Mexel^®432. Acute toxicity was highly dependent on the chemical and species tested. NaClO presented more toxic effects than Mexel^®432, also B. plicatilis was the most sensitive species in both cases. The lowest NOECs obtained, 0.25 mg/L for NaClO and 2.12 mg/L for Mexel^®432, were similar to the theoretical residual concentrations of these biocides in cooling water discharges. Therefore, these discharges can cause undesirable negative effects upon the aquatic organisms present.     

Potential enzyme toxicity of oxytetracycline to catalase

Oxytetracycline (OTC) is a kind of widely used veterinary drugs. The residue of OTC in the environment is potentially harmful. In the present work, the non-covalent toxic interaction of OTC with catalase was investigated by the fluorescence spectroscopy, UV-vis absorption and circular dichroism (CD) spectroscopy at physiological pH 7.4. OTC can interact with catalase to form a complex mainly by van der Waals' interactions and hydrogen bonds with one binding site. The association constants K were determined to be K_293K = 7.09 × 10⁴ L mol^− 1 and K_311K = 3.31 × 10⁴ L mol^− 1. The thermodynamic parameters (ΔH°, ΔG° and ΔS°) of the interaction were calculated. Based on the Förster theory of non-radiative energy transfer, the distance between bound OTC and the tryptophan residues of catalase was determined to be 6.48 nm. The binding of OTC can result in change of the micro-environment of the tryptophan residues and the secondary structure of catalase. The activity of catalase was also inhibited for the bound OTC. This work establishes a new strategy to probe the enzyme toxicity of veterinary drug residues and is helpful for clarifying the molecular toxic mechanism of OTC in vivo. The established strategy can be used to investigate the potential enzyme toxicity of other small organic pollutants and drugs.     

Synthesis of monodispersed CMC-stabilized Fe-Cu bimetal nanoparticles for in situ reductive dechlorination of 1,2,4-trichlorobenzene

Monodispersed carboxymethyl cellulose (CMC)-stabilized Fe-Cu bimetal nanoparticles with an average diameter of less than 20 nm were successfully synthesized by a modified water-based approach. The as-resulting particles exhibit a core-shell structure and are quite uniform in size and shape. Batch experiments demonstrated that these nanoparticles could effectively dechlorinate 1,2,4-trichlorobenzene (1,2,4-TCB). Near 90% of reduction efficiency was achieved by CMC-stabilized Fe-Cu for 24 h treatment. By monitoring the reaction products with time by GC-MS, it was found that 1,2,4-TCB transformation mainly followed the sequential hydrogenolysis to 1,2-dichlorobenzene (12DCB), then chlorobenzene (CB) and eventually benzene. The pseudo first order 1,2,4-TCB degradation rate were 0.09 h⁻¹ and 0.06 h⁻¹ as CMC-to-Fe molar ratios were 0.00248 and 0.00124, respectively. Dechlorination mechanism was also proposed in this study.     

Comparative toxicity of single and combined mixtures of selected pollutants among larval stages of the native freshwater mussels (Unio elongatulus) and the invasive zebra mussel (Dreissena polymorpha)

This study evaluated the impact of biocides (tributyltin, chlorthalonil and Irgarol 1051) and of pollutants (copper, inorganic and methyl mercury and 4-nonylphenol) occurring in Ebro River (NE Spain) on early developmental stages of native Spanish freshwater and invasive zebra mussels. Toxicity tests were conducted with embryos and glochidia of zebra mussel (Dreissena polymorpha) and the naiad species Unio elongatulus, respectively. Toxicity was quantified in terms of median effective concentration (EC50) impairing embryogenesis and glochidia viability in single and combined mixture exposures. Irgarol 1051 was not toxic at concentrations below 40 × 10³ nM. Zebra mussel embryos were on average 50 fold more sensitive to the studied pollutants than glochidia. Tributyltin was the most toxic compound with EC50s for zebra mussel embryos and glochidia, respectively, of 1.24 and 47.93 nM, followed by chlorothalonil (3.65, 176.58 nM), methyl mercury (7.06, 156.4 nM), inorganic mercury (3.64, 518.28 nM), copper (19.73, 1358.55 nM) and 4-nonylphenol (33.99, 1221.48 nM). Combined toxicity of Ebro River pollutants (copper, inorganic and methyl mercury and 4-nonylphenol) was greater than additive in zebra mussel embryos and additive in glochidia. These results indicated that contaminant levels that affect zebra mussel embryos are not toxic to early life stages of the naiad mussel species U. elongatulus.     

Removal of airborne nanoparticles by membrane coated filters

The increasing amount of nanoparticles with the development of nanotechnology gives rise to concerns about potential negative impact on the environment and health hazards posed to humans. Membrane filter is an effective media to control nanoparticles. Three filters coated with polytetrafluoroethylene (PTFE) membrane were investigated in this study. A series of experiments on the filter efficiency and relevant parameters such as the particle size and face velocity were carried out. The data show that the efficiency curves for the membrane filters demonstrate the typical shape of “v” for particle sizes from 10 to 300 nm at face velocities from 0.3 to 15 cm/s. Membrane filters with larger pore sizes have larger Most Penetrating Particles Sizes (MPPS), and the MPPS decreases with increasing face velocity. The efficiencies decrease with increasing face velocity for particle sizes from 10 to 300 nm. We present the filtration efficiency data as a novel three-dimensional graph to illustrate its dependence on the particle size and face velocity. The membrane coated filter can be considered as two combined layers, one fibrous layer and one membrane layer. We develop a new filtration efficiency model which is a combination of the models for the two layers. Results from the model calculation agree with experimental data well. The study can help to optimize the filter product and to determine the operational parameters of filters, thus contributing to reduction of air pollution by rapidly emerging nanoparticles.     

Dechlorination kinetics of TCE at toxic TCE concentrations: Assessment of different models

The reductive dechlorination of trichloroethene (TCE) in a TCE source zone can be self-inhibited by TCE toxicity. A study was set up to examine the toxicity of TCE in terms of species specific degradation kinetics and microbial growth and to evaluate models that describe this self-inhibition. A batch experiment was performed using the TCE dechlorinating KB-1 culture at initial TCE concentrations ranging from 0.04 mM to saturation (8.4 mM). Biodegradation activity was highest at 0.3 mM TCE and no activity was found at concentrations from 4 to 8 mM. Species specific TCE and cis-DCE (cis-dichloroethene) degradation rates and Dehalococcoides numbers were modeled with Monod kinetics combined with either Haldane inhibition or a log-logistic dose-response inhibition on these rates. The log-logistic toxicity model appeared the most appropriate model and predicts that the species specific degradation activities are reduced by a factor 2 at about 1 mM TCE, respectively cis-DCE. However, the model showed that the inhibitive effects on the time for TCE to ethene degradation are a complex function of degradation kinetics and the initial cell densities of the dechlorinating species. Our analysis suggests that the self-inhibition on biodegradation cannot be predicted by a single concentration threshold without information on the cell densities.     

Photochemical reactivity of perfluorooctanoic acid (PFOA) in conditions representing surface water

Potential of perfluorooctanoic acid (PFOA) to degrade via indirect photolysis in aquatic solution under conditions representing surface water was studied. Globally distributed and bioaccumulative PFOA does not absorb solar radiation by itself, but may be potentially photochemically transformed by the natural sensitizers such as dissolved organic matter (DOM), nitrate or ferric iron. Reaction solutions containing purified water, fulvic acid (representing DOM), nitrate, ferric iron or sea water from the Baltic Sea were spiked with PFOA and irradiated with an artificial sun (290-800 nm). In comparison similar samples were also irradiated under UV radiation at 254 nm in order to study the direct photolysis. UV radiation at 254 nm decomposed PFOA to perfluoroheptanoic-, perfluorohexanoic- and perfluoropentanoic acids. The samples irradiated with an artificial sun contained no decomposition products and no decrease in PFOA concentration was observed. According to the detection limit of the products and typical solar radiation at the surface of ocean, the photochemical half-life for PFOA was estimated to be at least 256 years at the depth of 0 m, > 5000 years in the mixing layer of open ocean and > 25,000 years in coastal ocean. This is significantly more than the previously reported photochemical half-life of PFOA (> 0.96 years).     

Toxicity of 2,4-dinitrotoluene to terrestrial plants in natural soils

The presence of energetic materials (used as explosives and propellants) at contaminated sites is a growing international issue, particularly with respect to military base closures and demilitarization policies. Improved understanding of the ecotoxicological effects of these materials is needed in order to accurately assess the potential exposure risks and impacts on the environment and its ecosystems. We studied the toxicity of the nitroaromatic energetic material 2,4-dinitrotoluene (2,4-DNT) on alfalfa (Medicago sativa L.), barnyard grass (Echinochloa crusgalli L. Beauv.), and perennial ryegrass (Lolium perenne L.) using four natural soils varying in properties (organic matter, clay content, and pH) that were hypothesized to affect chemical bioavailability and toxicity. Amended soils were subjected to natural light conditions, and wetting and drying cycles in a greenhouse for 13 weeks prior to toxicity testing to approximate field exposure conditions in terms of bioavailability, transformation, and degradation of 2,4-DNT. Definitive toxicity tests were performed according to standard protocols. The median effective concentration (EC₅₀) values for shoot dry mass ranged from 8 to 229 mg kg^− 1, depending on the plant species and soil type. Data indicated that 2,4-DNT was most toxic in the Sassafras (SSL) and Teller (TSL) sandy loam soils, with EC₅₀ values for shoot dry mass ranging between 8 to 44 mg kg^− 1, and least toxic in the Webster clay loam soil, with EC₅₀ values for shoot dry mass ranging between 40 to 229 mg kg^− 1. The toxicity of 2,4-DNT for each of the plant species was significantly (p ≤ 0.05) and inversely correlated with the soil organic matter content. Toxicity benchmark values determined in the present studies for 2,4-DNT weathered-and-aged in SSL or TSL soils will contribute to development of an Ecological Soil Screening Level for terrestrial plants that can be used for ecological risk assessment at contaminated sites.     

Bacterial responses to Cu-doped TiO2 nanoparticles

The toxicity of Cu-doped TiO₂ nanoparticles (NPs, 20 nm), synthesized by a flame aerosol reactor, to Mycobacterium smegmatis and Shewanella oneidensis MR-1, is the primary focus of this study. Both doped and non-doped TiO₂ NPs (20 nm) tended to agglomerate in the medium solution, and therefore did not penetrate into the cell and damage cellular structures. TiO₂ particles (< 100 mg/L) did not apparently interfere with the growth of the two species in aqueous cultures. Cu-doped TiO₂ NPs (20 mg/L) significantly reduced the M. smegmatis growth rate by three fold, but did not affect S. oneidensis MR-1 growth. The toxicity of Cu-doped TiO₂ NPs was driven by the release of Cu²⁺ from the parent NPs. Compared to equivalent amounts of Cu²⁺, Cu-doped TiO₂ NPs exhibited higher levels of toxicity to M. smegmatis (P-value < 0.1). Addition of EDTA in the culture appeared to significantly decrease the anti-mycobacterium activity of Cu-doped TiO₂ NPs. S. oneidensis MR-1 produced a large amount of extracellular polymeric substances (EPS) under NP stress, especially extracellular protein. Therefore, S. oneidensis MR-1 was able to tolerate a much higher concentration of Cu²⁺ or Cu-doped TiO₂ NPs. S. oneidensis MR-1 also adsorbed NPs on cell surface and enzymatically reduced ionic copper in culture medium with a remediating rate of 61 µg/(liter?OD₆₀₀? hour) during its early exponential growth phase. Since the metal reducing Shewanella species can efficiently “clean” metal-oxide NPs, the activities of such environmentally relevant bacteria may be an important consideration for evaluating the ecological risk of metal-oxide NPs.