Distribution of potentially toxic elements (PTEs) in tailings,soils, and plants around Gol-E-Gohar iron mine,a case study in Iran

This study investigated the concentration of potentially toxic elements (PTEs) including Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, V, and Zn in 102 soils (in the Near and Far areas of the mine), 7 tailings, and 60 plant samples (shoots and roots of Artemisia sieberi and Zygophylum species) collected at the Gol-E-Gohar iron ore mine in Iran. The elemental concentrations in tailings and soil samples (in Near and Far areas) varied between 7.4 and 35.8 mg kg^?1 for As (with a mean of 25.39 mg kg^?1 for tailings), 7.9 and 261.5 mg kg^?1 (mean 189.83 mg kg^?1 for tailings) for Co, 17.7 and 885.03 mg kg^?1 (mean 472.77 mg kg^?1 for tailings) for Cu, 12,500 and 400,000 mg kg^?1 (mean 120,642.86 mg kg^?1 for tailings) for Fe, and 28.1 and 278.1 mg kg^?1 (mean 150.29 mg kg^?1 for tailings) for Ni. A number of physicochemical parameters and pollution index for soils were determined around the mine. Sequential extractions of tailings and soil samples indicated that Fe, Cr, and Co were the least mobile and that Mn, Zn, Cu, and As were potentially available for plants uptake. Similar to soil, the concentration of Al, As, Co, Cr, Cu, Fe, Mn, Mo, Ni, and Zn in plant samples decreased with the distance from the mining/processing areas. Data on plants showed that metal concentrations in shoots usually exceeded those in roots and varied significantly between the two investigated species (Artemisia sieberi > Zygophylum). All the reported results suggest that the soil and plants near the iron ore mine are contaminated with PTEs and that they can be potentially dispersed in the environment via aerosol transport and deposition.     

Copper bioaccumulation,photosystem II functioning,and oxidative stress in the seagrass <Emphasis Type="Italic">Cymodocea nodosa</Emphasis> exposed to copper oxide nanoparticles

Photosynthetic activity, oxidative stress, and Cu bioaccumulation in the seagrass Cymodocea nodosa were assessed 4, 12, 24, 48, and 72 h after exposure to two copper oxide nanoparticle (CuO NP) concentrations (5 and 10 mg L^?1). CuO NPs were characterized by scanning electron microscopy (SEM) and dynamic light scattering measurements (DLS). Chlorophyll fluorescence analysis was applied to detect photosystem II (PSII) functionality, while the Cu accumulation kinetics into the leaf blades was fitted to the Michaelis-Menten equation. The uptake kinetics was rapid during the first 4 h of exposure and reached an equilibrium state after 10 h exposure to 10 mg L^?1 and after 27 h to 5 mg L^?1 CuO NPs. As a result, 4-h treatment with 5 mg L^?1 CuO NPs, decreased the quantum yield of PS II photochemistry (Φ _PSΙΙ ) with a parallel increase in the regulated non-photochemical energy loss in PSII (Φ _NPQ ). However, the photoprotective dissipation of excess absorbed light energy as heat, through the process of non-photochemical quenching (NPQ), did not maintain the same fraction of open reaction centers (q _p ) as in control plants. This reduced number of open reaction centers resulted in a significant increase of H₂O₂ production in the leaf veins serving possibly as an antioxidant defense signal. Twenty-four-hour treatment had no significant effect on Φ _PSΙΙ and q _p compared to controls. However, 24 h exposure to 5 mg L^?1 CuO NPs increased the quantum yield of non-regulated energy loss in PSII (Φ _NO ), and thus the formation of singlet oxygen (¹O₂) via the triplet state of chlorophyll, possible because the uptake kinetics had not yet reached the equilibrium state as did 10 mg L^?1. Longer-duration treatment (48 and 72 h) had less effect on the allocation of absorbed light energy at PSII and the fraction of open reaction centers, compared to 4-h treatment, suggesting the function of a stress defense mechanism. The response of C. nodosa leaves to CuO NPs fits the “Threshold for Tolerance Model” with a threshold time (more than 4 h) required for induction of a stress defense mechanism, through H₂O₂ production.     

Photoassisted and photocatalytic degradation of sulfur mustard using TiO2 nanoparticles and polyoxometalates

The decomposition of highly toxic chemical warfare agent, sulfur mustard (bis(2-chloroethyl) sulfide or HD), has been studied by homogeneous photolysis and heterogeneous photocatalytic degradation on titania nanoparticles. Direct photolysis degradation of HD with irradiation system was investigated. The photocatalytic degradation of HD was investigated in the presence of TiO₂ nanoparticles and polyoxometalates embedded in titania nanoparticles in liquid phase at room temperature (33?±?2 °C). Degradation products during the treatment were identified by gas chromatography–mass spectrometry. Whereas apparent first-order kinetics of ultraviolet (UV) photolysis were slow (0.0091 min^?1), the highest degradation rate is obtained in the presence of TiO₂ nanoparticles as nanophotocatalyst. Simultaneous photolysis and photocatalysis under the full UV radiation leads to HD complete destruction in 3 h. No degradation products observed in the presence of nanophotocatalyst without irradiation in 3 h. It was found that up to 90 % of agent was decomposed under of UV irradiation without TiO₂, in 6 h. The decontamination mechanisms are often quite complex and multiple mechanisms can be operable such as hydrolysis, oxidation, and elimination. By simultaneously carrying out photolysis and photocatalysis in hexane, we have succeeded in achieving faster HD decontamination after 90 min with low catalyst loading. TiO₂ nanoparticles proved to be a superior photocatalyst under UV irradiation for HD decontamination.     

Photolysis of pharmaceuticals and personal care products in the marine environment under simulated sunlight conditions: irradiation and identification

The photochemical fate of 16 pharmaceuticals and personal care products (PPCPs) found in the environment has been studied under controlled laboratory conditions applying a sunlight simulator. Aqueous samples containing PPCPs at environmentally relevant concentrations were extracted by solid-phase extraction (SPE) after irradiation. The exposed extracts were subsequently analysed by liquid chromatography combined with triple quadrupole mass spectrometry (HPLC-MS/MS) for studying the kinetics of photolytic transformations. Almost all exposed PPCPs appeared to react with a half-life time (τ _1/2) of less than 30 min. For ranitidine, sulfamethoxazole, diclofenac, warfarin, sulfamethoxazole and ciprofloxacin, τ_1/2 was found to be even less than 5 min. The structures of major photolysis products were determined using quadrupole-time-of-flight mass spectrometry (QToF) and spectroscopic data reported in the literature. For diclofenac, the transformation products carbazol-1-yl-acidic acid and 8-chloro-9H-carbazol-1-yl-acetic acid were identified based on the mass/charge ratio of protonated ions and their fragmentation pattern in negative electrospray ionization (ESI^?-QTOF). Irradiation of carbamazepine resulted in three known products: acridine, carbamazepine-10,11-epoxide, and 10,11-dihydro-10,11-dihydroxy-carbamazepine, whereas acetaminophen was photolytically transformed to 1-(2-amino-5 hydroxyphenyl) ethenone. These photochemical products were subsequently identified in seawater or fish samples collected at sites exposed to wastewater effluents on the Saudi Arabian coast of the Red Sea.     

Natural deep eutectic solvent mediated pretreatment of rice straw: bioanalytical characterization of lignin extract and enzymatic hydrolysis of pretreated biomass residue

The present investigation demonstrated pretreatment of lignocellulosic biomass rice straw using natural deep eutectic solvents (NADESs), and separation of high-quality lignin and holocellulose in a single step. Qualitative analysis of the NADES extract showed that the extracted lignin was of high purity (>90 %), and quantitative analysis showed that nearly 60?±?5 % (w/w) of total lignin was separated from the lignocellulosic biomass. Addition of 5.0 % (v/v) water during pretreatment significantly enhanced the total lignin extraction, and nearly 22?±?3 % more lignin was released from the residual biomass into the NADES extract. X-ray diffraction studies of the untreated and pretreated rice straw biomass showed that the crystallinity index ratio was marginally decreased from 46.4 to 44.3 %, indicating subtle structural alterations in the crystalline and amorphous regions of the cellulosic fractions. Thermogravimetric analysis of the pretreated biomass residue revealed a slightly higher T _dcp (295 °C) compared to the T _dcp (285 °C) of untreated biomass. Among the tested NADES reagents, lactic acid/choline chloride at molar ratio of 5:1 extracted maximum lignin of 68?±?4 mg g^?1 from the rice straw biomass, and subsequent enzymatic hydrolysis of the residual holocellulose enriched biomass showed maximum reducing sugars of 333?±?11 mg g^?1 with a saccharification efficiency of 36.0?±?3.2 % in 24 h at 10 % solids loading.     

Accumulation of Cr,Cd, Pb,Cu, and Zn by plants in tanning sludge storage sites: opportunities for contamination bioindication and phytoremediation

Tanning sludge enriched with high concentrations of Cr and other metals has adverse effects on the environment. Plants growing in the metalliferous soils may have the ability to cope with high metal concentrations. This study focuses on potentials of using native plants for bioindication and/or phytoremediation of Cr-contaminated sites. In the study, we characterized plants and soils from six tanning sludge storage sites. Soil in these sites exhibited toxic levels of Cr (averaged 16,492 mg kg^?1) and other metals (e.g., 48.3 mg Cu kg^?1, 2370 mg Zn kg^?1, 44.9 mg Pb kg^?1, and 0.59 mg Cd kg^?1). Different metal tolerance and accumulation patterns were observed among the sampled plant species. Phragmites australis, Zephyranthes candida, Cynodon dactylon, and Alternanthera philoxeroides accumulated moderate-high concentrations of Cr and other metals, which could make them good bioindicators of heavy metal pollution. High Cr and other metal concentrations (e.g., Cd and Pb) were found in Chenopodium rubrum (372 mg Cr kg^?1), Aster subulatus (310 mg Cr kg^?1), and Brassica chinensis (300 mg Cr kg^?1), being considered as metal accumulators. In addition, Nerium indicum and Z. candida were able to tolerate high concentrations of Cr and other metals, and they may be used as preferable pioneer species to grow or use for restoration in Cr-contaminated sites. This study can be useful for establishing guidelines to select the most suitable plant species to revegetate and remediate metals in tanning sludge-contaminated fields.     

Solar CPC pilot plant photocatalytic degradation of bisphenol A in waters and wastewaters using suspended and supported-TiO2. Influence of photogenerated species

Photocatalytic degradation of bisphenol A (BPA) in waters and wastewaters in the presence of titanium dioxide (TiO₂) was performed under different conditions. Suspensions of the TiO₂ were used to compare the degradation efficiency of BPA (20 mg L^?1) in batch and compound parabolic collector (CPC) reactors. A TiO₂ catalyst supported on glass spheres was prepared (sol–gel method) and used in a CPC solar pilot plant for the photodegradation of BPA (100 μg L^?1). The influence of OH·, O₂ ^·?, and h ⁺ on the BPA degradation were evaluated. The radicals OH· and O₂ ^·? were proved to be the main species involved on BPA photodegradation. Total organic carbon (TOC) and carboxylic acids were determined to evaluate the BPA mineralization during the photodegradation process. Some toxicological effects of BPA and its photoproducts on Eisenia andrei earthworms were evaluated. The results show that the optimal concentration of suspended TiO₂ to degrade BPA in batch or CPC reactors was 0.1 g L^?1. According to biological tests, the BPA LC₅₀ in 24 h for E. andrei was of 1.7?×?10^?2 mg cm^?2. The photocatalytic degradation of BPA mediated by TiO₂ supported on glass spheres suffered strong influence of the water matrix. On real municipal wastewater treatment plant (MWWTP) secondary effluent, 30 % of BPA remains in solution; nevertheless, the method has the enormous advantage since it eliminates the need of catalyst removal step, reducing the cost of treatment.     

Non-enhanced phytoextraction of cadmium,zinc, and lead by high-yielding crops

Heavy metal soil contamination from mining and smelting has been reported in several regions around the world, and phytoextraction, using plants to accumulate risk elements in aboveground harvestable organs, is a useful method of substantially reducing this contamination. In our 3-year experiment, we tested the hypothesis that phytoextraction can be successful in local soil conditions without external fertilizer input. The phytoextraction efficiency of 15 high-yielding crop species was assessed in a field experiment performed at the Litavka River alluvium in the P?íbram region of Czechia. This area is heavily polluted by Cd, Zn, and Pb from smelter installations which also polluted the river water and flood sediments. Heavy metal concentrations were analyzed in the herbaceous plants’ aboveground and belowground biomass and in woody plants’ leaves and branches. The highest Cd and Zn mean concentrations in the aboveground biomass were recorded in Salix x fragilis L. (10.14 and 343 mg kg^?1 in twigs and 16.74 and 1188 mg kg^?1 in leaves, respectively). The heavy metal content in woody plants was significantly higher in leaves than in twigs. In addition, Malva verticillata L. had the highest Cd, Pb, and Zn concentrations in herbaceous species (6.26, 12.44, and 207 mg kg^?1, respectively). The calculated heavy metal removal capacities in this study proved high phytoextraction efficiency in woody species; especially for Salix × fragilis L. In other tested plants, Sorghum bicolor L., Helianthus tuberosus L., Miscanthus sinensis Andersson, and Phalaris arundinacea L. species are also recommended for phytoextraction.     

Photocatalytic Degradation of an Organophosphorus Pesticide Phosalone in Aqueous Suspensions of Titanium Dioxide

Abstract

The present work deals with photocatalytic degradation of an organophosphorus pesticide, phosalone, in water in the presence of TiO₂ particles under UV light illumination (1000 W). The influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO₂, irradiation time, stirring rate, and distance from UV source, on the photodegradation efficiency of phosalone was investigated. The degradation rate of phosalone was not high when the photolysis was carried out in the absence of TiO₂ and it was negligible in the absence of UV light. The half-life (DT₅₀) of a 20 ppm aqueous solution of phosalone was 15 min in optimized conditions. The plot of lnC (phosalone) vs. time was linear, suggesting first order reaction (K = 0.0532 min^?1). The half-life time of photomineralization in the concentration range of 7.5–20 ppm was 13.02 min. The efficiency of the method was also determined by measuring the reduction of Chemical Oxygen Demand (COD). During the mineralization under optimized conditions, COD decreased by more than 45% at irradiation time of 15 min. The photodegradation of phosalone was enhanced by addition of proper amount of hydrogen peroxide (150 ppm).     

Visible light photocatalytic antibacterial activity of Ni-doped and N-doped TiO<Subscript>2</Subscript> on <Emphasis Type="Italic">Staphylococcus aureus</Emphasis> and <Emphasis Type="Italic">Escherichia coli</Emphasis> bacteria

The Ni-doped and N-doped TiO₂ nanoparticles were investigated for their antibacterial activities on Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) bacteria. Their morphological features and characteristics such as particle size, surface area, and visible light absorbing capacity were compared and discussed. Scanning electron microscopy, X-ray diffraction, and UV–visible spectrophotometry were used to characterize both materials. The inactivation of E. coli (as an example of Gram-negative bacteria) and S. aureus (as an example of Gram-positive bacteria) with Ni-doped and N-doped TiO₂ was investigated in the absence and presence of visible light. Antibacterial activity tests were conducted using undoped, Ni-doped, and N-doped TiO₂. The N-doped TiO₂ nanoparticles show higher antibacterial activity than Ni-doped TiO₂. The band gap narrowing of N-doped TiO₂ can induce more visible light absorption and leads to the superb antibacterial properties of this material. The complete inactivation time for E. coli at an initial cell concentration of 2.7?×?10⁴ CFU/mL was 420 min which is longer than the 360 min required for S. aureus inactivation. The rate of inactivation of S. aureus using the doped TiO₂ nanoparticles in the presence of visible light is greater than that of E. coli. The median lethal dose (LD50) values of S. aureus and E. coli by antibacterial activity under an 18-W visible light intensity were 80 and 350 mg/ml for N-doped TiO₂, respectively.     

Effects of realistic concentrations of TiO<Subscript>2</Subscript> and ZnO nanoparticles in <Emphasis Type="Italic">Prochilodus lineatus</Emphasis> juvenile fish

The impact of nanoparticles on fish health is still a matter of debate, since nanotechnology is quite recent. In this study, freshwater benthonic juvenile fish Prochilodus lineatus were exposed through water to three concentrations of TiO₂ (0.1, 1, and 10 μg l^?1) and ZnO (7, 70, and 700 μg l^?1) nanoparticles, as well as to a mixture of both (TiO₂ 1 μg l^?1?+?ZnO 70 μg l^?1) for 5 and 30 days. Nanoparticle characterization revealed an increase of aggregate size in the function of concentration, but suspensions were generally stable. Fish mortality was high at subchronic exposure to 70 and 700 μg l^?1 of ZnO. Nanoparticle exposure led to decreased acetylcholinesterase activity either in the muscle or in the brain, depending on particle composition (muscle—TiO₂ 10 μg l^?1; brain—ZnO 7 and 700 μg l^?1), and protein oxidative damage increased in the brain (ZnO 70 μg l^?1) and gills (ZnO 70 μg l^?1 and mixture) but not in the liver. Exposed fish had more frequent alterations in the liver (necrosis, vascular congestion, leukocyte infiltration, and basophilic foci) and gills (hyperplasia and epithelial damages, e.g., epithelial disorganization and epithelial loss) than the control fish. Thus, predicted concentrations of TiO₂ and ZnO nanoparticles caused detectable effects on P. lineatus that may have important consequences to fish health. But, these effects are much more subtle than those usually reported in the scientific literature for high concentrations or doses of metal nanoparticles.     

Accelerated photo-transformation of 2,2′,4,4′,5,5′-hexachlorobiphenyl (PCB 153) in water by dissolved organic matter

The ubiquitous dissolved organic matter (DOM) has an important influence on transformation of organic contaminants through the production of reactive substances, such as ^?OH, ¹O₂, and ³DOM*. The photolysis of a higher chlorinated polychlorinated biphenyl (PCB) congener (2,2′,4,4′,5,5′-hexachlorobiphenyl, PCB 153) under simulated sunlight in presence of humic acid (HA) was investigated. Degradation of PCB 153 was accelerated significantly by the addition of HA, with a rate constant of 0.0214, 0.0413, and 0.0358 h^?1 in the initial 18 h of irradiation in presence of 1, 5, and 20 mg/L HA, respectively. The main photodegradation products analyzed by gas chromatography mass spectrometry were 4-hydroxy-2,2′,4′,5,5′-pentaCB and 2,4,5-trichlorobenzoic acid. Main reactive species involved were determined by the electron spin-resonance spectroscopy, including ¹O₂ and ^?OH. Special scavengers were added to elucidate the photolysis mechanisms. By using the specific scavengers, it turned out that ^?OH accounted for 29.3 % of the degradation, and the intra-DOM reactive species (¹O₂, ^?OH, and ³DOM*) accounted for 59.6 % of the degradation. Photo-transformation sensitized by DOM, which involves both aqueous and intra-DOM reactions of PCBs with reactive species, may be one of the most important mechanisms for natural attenuation of PCBs.     

Cr(VI) and COD removal from landfill leachate by polyculture constructed wetland at a pilot scale

Four subsurface horizontal-flow constructed wetlands (CWs) at a pilot scale planted with a polyculture of the tropical plants Gynerium sagittatum (Gs), Colocasia esculenta (Ce) and Heliconia psittacorum (He) were evaluated for 7 months. The CW cells with an area of 17.94 m² and 0.60 m (h) each and 0.5 m of gravel were operated at continuous gravity flow (Q?=?0.5 m³ day^?1) and a theoretical HRT of 7 days each and treating landfill leachate for the removal of filtered chemical oxygen demand (COD_f), BOD₅, TKN, NH₄ ⁺, NO₃ ^?, PO₄ ^3?–P and Cr(VI). Three CWs were divided into three sections, and each section (5.98 m²) was seeded with 36 cuttings of each species (plant density of six cuttings per square metre). The other unit was planted randomly. The final distributions of plants in the bioreactors were as follows: CW I (He-Ce-Gs), CW II (randomly), CW III (Ce-Gs-He) and CW IV (Gs-He-Ce). The units received effluent from a high-rate anaerobic pond (BLAAT®). The results show a slightly alkaline and anoxic environment in the solid-liquid matrix (pH?=?8.0; 0.5–2 mg L^?1 dissolved oxygen (DO)). COD_f removal was 67 %, BOD₅ 80 %, and TKN and NH₄ ⁺ 50–57 %; NO₃ ^? effluents were slightly higher than the influent, PO₄ ^3?–P (38 %) and Cr(VI) between 50 and 58 %. CW IV gave the best performance, indicating that plant distribution may affect the removal capacity of the bioreactors. He and Gs were the plants exhibiting a translocation factor (TF) of Cr(VI) >1. The evaluated plants demonstrated their suitability for phytoremediation of landfill leachate, and all of them can be categorized as Cr(VI) accumulators. The CWs also showed that they could be a low-cost operation as a secondary system for treatment of intermediated landfill leachate (LL).     

Photodegradation of 4-tert octylphenol in aqueous solution promoted by Fe(III)

4-Tert-octylphenol (4-t-OP), a kind of endocrine-disrupting compounds, is widely distributed in natural water surroundings but can hardly be biodegraded. The advanced oxidation processes (AOPs) have been proved to be an efficient method to degrade 4-t-OP. In this study, the photodegradation of 4-t-OP in aqueous solution promoted by Fe(III) and the photooxidation mechanism were investigated. The ferric perchlorate was added into the aqueous solution for the production of hydroxyl radical. The efficiency of mineralization was monitored by total organic carbon analyzer, and photooxidation products were determined by high-performance liquid chromatography and liquid chromatography-mass spectrometer. 4-t-OP (2.4?×?10^?5 M) in aqueous solution was completely degraded after 45 min in the presence of Fe(III) (1.2?×?10^?3 M) under UV irradiation (λ?=?365 nm). The optimal pH was 3.5. Higher Fe(III) concentration or lower initial 4-t-OP concentration led to increased photodegradation efficiency of 4-t-OP. The reaction was almost completely inhibited in the presence of 2-propanol. About 70 % mineralization of the solution was obtained after 50 h. The photooxidation product was supposed to be 4-tert-octyl catechol. 4-t-OP in aqueous solution can be degraded in the presence of Fe(III) under the solar irradiation. The photoinduced degradation is due to the reaction with hydroxyl radicals. It shows that the 4-t-OP is mineralized by the inducement of Fe(III) aquacomplexes, which exposes to solar light. Therefore, the results would provide useful information for the potential application of the AOPs to remove 4-t-OP in water surroundings.     

Plant responses to a phytomanaged urban technosol contaminated by trace elements and polycyclic aromatic hydrocarbons

Medicago sativa was cultivated at a former harbor facility near Bordeaux (France) to phytomanage a soil contaminated by trace elements (TE) and polycyclic aromatic hydrocarbons (PAH). In parallel, a biotest with Phaseolus vulgaris was carried out on potted soils from 18 sub-sites to assess their phytotoxicity. Total soil TE and PAH concentrations, TE concentrations in the soil pore water, the foliar ionome of M. sativa (at the end of the first growth season) and of Populus nigra growing in situ, the root and shoot biomass and the foliar ionome of P. vulgaris were determined. Despite high total soil TE, soluble TE concentrations were generally low, mainly due to alkaline soil pH (7.8–8.6). Shoot dry weight (DW) yield and foliar ionome of P. vulgaris did not reflect the soil contamination, but its root DW yield decreased at highest soil TE and/or PAH concentrations. Foliar ionomes of M. sativa and P. nigra growing in situ were generally similar to the ones at uncontaminated sites. M. sativa contributed to bioavailable TE stripping by shoot removal (in g ha^?1 harvest^?1): As 0.9, Cd 0.3, Cr 0.4, Cu 16.1, Ni 2.6, Pb 4, and Zn 134. After 1 year, 72 plant species were identified in the plant community across three subsets: (I) plant community developed on bare soil sowed with M. sativa; (II) plant community developed in unharvested plots dominated by grasses; and (III) plant community developed on unsowed bare soil. The shoot DW yield (in mg ha^?1 harvest^?1) varied from 1.1 (subset I) to 6.9 (subset II). For subset III, the specific richness was the lowest in plots with the highest phytotoxicity for P. vulgaris.     

Triclocarban: UV photolysis,wastewater disinfection,and ecotoxicity assessment using molecular biomarkers

Triclocarban (TCC) is an antibacterial agent found in pharmaceuticals and personal care products (PPCP). It is potentially bioaccumulative and an endocrine disruptor, being classified as a contaminant of emerging concern (CEC). In normal uses, approximately 96% of the used TCC can be washed down the drain going into the sewer system and eventually enter in the aquatic environment. UV photolysis can be used to photodegrade TCC and ecotoxicity assays could indicate the photodegradation efficiency, since the enormous structural diversity of photoproducts and their low concentrations do not always allow to identify and quantify them. In this work, the TCC was efficiently degraded by UVC direct photolysis and the ecotoxicity of the UV-treated mixtures was investigated. Bioassays indicates that Daphnia similis (48 h EC₅₀ = 0.044 μM) was more sensitive to TCC than Pseudokirchneriella subcapitata (72 h IC₅₀ = 1.01 μM). TCC and its photoproducts caused significant effects on Eisenia andrei biochemical responses (catalase and glutathione-S-transferase); 48 h was a critical exposure time, since GST reached the highest activity values. UVC reduced the TCC toxic effect after 120 min. Furthermore, TCC was photodegraded in domestic wastewater which was simultaneously disinfected for total coliform bacterial (TCB) (360 min) and Escherichia coli (60 min).

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Graphical abstract TCC degradation and ecotoxicological assessment

     

Effects of sediment burial disturbance on macro and microelement dynamics in decomposing litter of <Emphasis Type="Italic">Phragmites australis</Emphasis> in the coastal marsh of the Yellow River estuary,China

From April 2008 to November 2009, a field decomposition experiment was conducted to investigate the effects of sediment burial on macro (C, N) and microelement (Pb, Cr, Cu, Zn, Ni, and Mn) variations in decomposing litter of Phragmites australis in the coastal marsh of the Yellow River estuary. Three one-off sediment burial treatments [no sediment burial (0 mm year^?1, S₀), current sediment burial (100 mm year^?1, S₁₀), and strong sediment burial (200 mm year^?1, S₂₀)] were laid in different decomposition sites. Results showed that sediment burials showed significant influence on the decomposition rate of P. australis, in the order of S₁₀ (0.001990 day^?1)?≈?S₂₀ (0.001710 day^?1)?>?S₀ (0.000768 day^?1) (p?<?0.05). The macro and microelement in decomposing litters of the three burial depths exhibited different temporal variations except for Cu, Zn, and Ni. No significant differences in C, N, Pb, Cr, Zn, and Mn concentrations were observed among the three burial treatments except for Cu and Ni (p?>?0.05). With increasing burial depth, N, Cr, Cu, Ni, and Mn concentrations generally increased, while C, Pb, and Zn concentrations varied insignificantly. Sediment burial was favorable for C and N release from P. australis, and, with increasing burial depth, the C release from litter significantly increased, and the N in litter shifted from accumulation to release. With a few exceptions, Pb, Cr, Zn, and Mn stocks in P. australis in the three treatments evidenced the export of metals from litter to environment, and, with increasing burial depth, the export amounts increased greatly. Stocks of Cu and Ni in P. australis in the S₁₀ and S₂₀ treatments were generally positive, evidencing incorporation of the two metals in most sampling times. Except for Ni, the variations of C, N, Pb, Cr, Cu, Zn, and Mn stocks in P. australis in the S₁₀ and S₂₀ treatments were approximated, indicating that the strong burial episodes (S₂₀) occurred in P. australis marsh in the future would have little influence on the stocks of these elements. With increasing burial depths, the P. australis was particularly efficient in binding Cu and Ni and releasing C, N, Pb, Cr, Zn, and Mn, implying that the potential eco-toxic risk of Pb, Cr, Zn, and Mn exposure might be very serious. This study emphasized the effects of different burials on nutrient and metal cycling and mass balance in the P. australis marsh of the Yellow River estuary.     

Assessment of solar driven TiO2-assisted photocatalysis efficiency on amoxicillin degradation

The objective of this work was to evaluate the efficiency of a solar TiO₂-assisted photocatalytic process on amoxicillin (AMX) degradation, an antibiotic widely used in human and veterinary medicine. Firstly, solar photolysis of AMX was compared with solar photocatalysis in a compound parabolic collectors pilot scale photoreactor to assess the amount of accumulated UV energy in the system (Q _UV) necessary to remove 20 mg L^?1 AMX from aqueous solution and mineralize the intermediary by-products. Another experiment was also carried out to accurately follow the antibacterial activity against Escherichia coli DSM 1103 and Staphylococcus aureus DSM 1104 and mineralization of AMX by tracing the contents of dissolved organic carbon (DOC), low molecular weight carboxylate anions, and inorganic anions. Finally, the influence of individual inorganic ions on AMX photocatalytic degradation efficiency and the involvement of some reactive oxygen species were also assessed. Photolysis was shown to be completely ineffective, while only 3.1 kJ_UV?L^?1 was sufficient to fully degrade 20 mg L^?1 AMX and remove 61 % of initial DOC content in the presence of the photocatalyst and sunlight. In the experiment with an initial AMX concentration of 40 mg L^?1, antibacterial activity of the solution was considerably reduced after elimination of AMX to levels below the respective detection limit. After 11.7 kJ_UV?L^?1, DOC decreased by 71 %; 30 % of the AMX nitrogen was converted into ammonium and all sulfur compounds were converted into sulfate. A large percentage of the remaining DOC was in the form of low molecular weight carboxylic acids. Presence of phosphate ions promoted the removal of AMX from solution, while no sizeable effects on the kinetics were found for other inorganic ions. Although the AMX degradation was mainly attributed to hydroxyl radicals, singlet oxygen also plays an important role in AMX self-photosensitization under UV/visible solar light.     

Transformation of sulfaquinoxaline by chlorine and UV light in water: kinetics and by-product identification

Sulfaquinoxaline (SQX) is an antimicrobial of the sulfonamide class, frequently detected at low levels in drinking and surface water as organic micropollutant. The main goal of the present study is the evaluation of SQX reactivity during chlorination and UV irradiations which are two processes mainly used in water treatment plants. The SQX transformation by chlorination and UV lights (254 nm) was investigated in purified water at common conditions used for water disinfection (pH =?7.2, temperature =?25 °C, [chlorine] =?3 mg L^?1). The result shows a slow degradation of SQX during photolysis compared with chlorination process. Kinetic studies that fitted a fluence-based first-order kinetic model were used to determine the kinetic constants of SQX degradation; they were equal to 0.7?×?10^?4 and 0.7?×?10^?2 s^?1corresponding to the half time lives of 162 and 1.64 min during photolysis and chlorination, respectively. In the second step, seven by-products were generated during a chlorination and photo-transformation of SQX and identified using liquid chromatography with electrospray ionization and tandem mass spectrometry (MS-MS). SO₂ extrusion and direct decomposition were the common degradation pathway during photolysis and chlorination. Hydroxylation and isomerization were observed during photodegradation only while electrophilic substitution was observed during chlorination process.     

Start-up of sequencing batch reactor with <Emphasis Type="Italic">Thiosphaera pantotropha</Emphasis> for treatment of high-strength nitrogenous wastewater and sludge characterization

Biological treatment of high-strength nitrogenous wastewater is challenging due to low growth rate of autotrophic nitrifiers. This study reports bioaugmentation of Thiosphaera pantotropha capable of simultaneously performing heterotrophic nitrification and aerobic denitrification (SND) in sequencing batch reactors (SBRs). SBRs fed with 1:1 organic-nitrogen (N) and NH₄ ⁺-N were started up with activated sludge and T. pantotropha by gradual increase in N concentration. Sludge bulking problems initially observed could be overcome through improved aeration and mixing and change in carbon source. N removal decreased with increase in initial nitrogen concentration, and only 50–60 % removal could be achieved at the highest N concentration of 1000 mg L^?1 at 12-h cycle time. SND accounted for 28 % nitrogen loss. Reducing the settling time to 5–10 min and addition of divalent metal ions gradually improved the settling characteristics of sludge. Sludge aggregates of 0.05–0.2 mm diameter, much smaller than typical aerobic granules, were formed and progressive increase in settling velocity, specific gravity, Ca²⁺, Mg²⁺, protein, and polysaccharides was observed over time. Granulation facilitated total nitrogen (TN) removal at a constant rate over the entire 12-h cycle and thus increased TN removal up to 70 %. Concentrations of NO₂ ^?-N and NO₃ ^?-N were consistently low indicating effective denitrification. Nitrogen removal was possibly limited by urea hydrolysis/nitrification. Presence of T. pantotropha in the SBRs was confirmed through biochemical tests and 16S rDNA analysis.