Photocatalytic removal of organic pollutants in aqueous solution by Bi(4)Nb(x)Ta((1-x))O(8)I

In this work, Bi₄Nb_xTa_(1−x)O₈I photocatalysts have been synthesized by solid state reaction method and characterized by powder X-ray diffraction, scanning electron microscope and UV-Vis near infrared diffuse reflectance spectroscopy. The photocatalytic activity of these photocatalysts was evaluated by the degradation of methyl orange (MO) in aqueous solutions under visible light, UV light and solar irradiation. The effects of catalyst dosage, initial pH and MO concentration on the removal efficiency were studied, and the photocatalytic reaction kinetics of MO degradation as well. The results indicated that Bi₄Nb_xTa_(1−x)O₈I exhibited high photocatalytic activity for the removal of MO in aqueous solutions. For example, the removal efficiency of MO by Bi₄Nb_0.1Ta_0.9O₈I was as high as 92% within 12 h visible light irradiation under the optimal conditions: initial MO concentration of 5-10 mg L⁻¹, catalyst dosage of 6 g L⁻¹ and natural pH (6-8), the MO molecules could be completely degradated by Bi₄Nb_0.1Ta_0.9O₈I within 40 min under UV light irradiation, and the photodegradation efficiency reaches to 60% after 7 h solar irradiation. Furthermore, the photocatalytic degradation of Bisphenol A (BPA) was also investigated under visible light irradiation. It is found that 99% BPA could be mineralized by Bi₄Nb_0.1Ta_0.9O₈I after 16 h visible light irradiation. Through HPLC/MS, BOD, TOC, UV-Vis measurements, we determined possible degradation products of MO and BPA. The results indicated that MO was degradated into products which are easier to be biodegradable and innocuous treated, and BPA could be mineralized completely. Furthermore, the possibility for the photosensitization effect in the degradation process of MO under visible light irradiation has been excluded.     

Metabolites of 2,2'-dichlorobiphenyl and 2,6-dichlorobiphenyl in hairy root culture of black nightshade Solanum nigrum SNC-9O

The hairy root culture of black nightshade (Solanum nigrum) SNC-9O was exposed to 2,2′-dichlorobiphenyl (PCB 4) and 2,6-dichlorobiphenyl (PCB 10) to follow the metabolites produced. The analytical standards of 4-hydroxy-2,2′-dichlorobiphenyl, 5′-hydroxy-2,2′-dichlorobiphenyl, 4-hydroxy-2,6-dichlorobiphenyl, 2-hydroxy-2′,6′-dichlorobiphenyl, 3-hydroxy-2′,6′-dichlorobiphenyl and 4-hydroxy-2′,6′-dichlorobiphenyl have been synthesized. Hydroxy-metabolites of both PCB 4 and PCB 10 were present in the biomass. These appeared mainly as conjugates rather than as free hydroxy-PCBs, both maintained in plant cells. The concentrations of non-conjugated hydroxy-PCBs ranged between 0.9 and 35.2 μg kg⁻¹ of biomass fresh weight and the concentration of the conjugated ones ranged between 2.0 and 113.0 μg kg⁻¹ depending on the position of hydroxyl. The para- position of biphenyl (4 or 4′) seems to be preferred for hydroxylation. Methoxy-PCBs and hydroxy-methoxy-PCBs have also been identified in plant cells. Hydroxyl in the meta-position (3, 3′, 5 or 5′) appears to be preferred for methylation in hydroxy-PCBs. Hydroxy-methoxy-PCBs have occurred in the conjugated form as well.     

Studies on atmospheric degradation of diazinon in the EUPHORE simulation chamber

The gas phase atmospheric degradation of diazinon has been investigated at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. The rate constant for reaction of diazinon with OH radicals was measured using a conventional relative rate method with di-n-buthylether as reference compound being k = (3.5 ± 1.2) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ at 302 ± 10 K and atmospheric pressure. The available evidence indicates that tropospheric degradation of diazinon is mainly controlled by reaction with OH radicals, and that the tropospheric lifetime with respect to the OH reaction is estimated to be around 4 h whereas its lifetime with respect to the photolysis is higher than 1 d under our conditions. Significant aerosol formation was observed following the reaction of diazinon with OH radicals, and the main carbon-containing products detected in the particle phase were hydroxydiazinon, hydroxydiazoxon and 2-isopropyl-6-methyl-pyrimidinyl-4-ol.     

Heterogeneous photocatalytic oxidation of cyprodinil and fludioxonil in leaching water under solar irradiation

The efficiency of ZnO and TiO₂ suspensions in the photocatalytic degradation of two fungicides (cyprodinil and fludioxonil) in leaching water was investigated. The experiments were carried out at pilot plant scale using compound parabolic collectors under natural sunlight. The blank experiments for both irradiated compounds solutions showed that both oxides strongly enhanced the removal of the fungicides. The addition of an oxidant (Na₂S₂O₈) to the ZnO or TiO₂ increased the rate of photooxidation. The degradation of cyprodinil and fludioxonil followed first order kinetics according to the Langmuir-Hinshelwood model. Complete degradation of both fungicides was achieved within 4 h (t_30W = 18 min) when treated with illuminated ZnO. The disappearance time (DT₇₅), when referred to the normalized illumination time (t_30W), was lower than 40 and 550 min (t_30W = 2 and 40 min) for both fungicides using ZnO or TiO₂, respectively. ZnO appeared to be more effective in cyprodinil and fludioxonil oxidation than TiO₂ probably due to its nonstoichiometry.     

Aerobic degradation of tetrabromobisphenol-A by microbes in river sediment

This study investigated the aerobic degradation of tetrabromobisphenol-A (TBBPA) and changes in the microbial community in river sediment from southern Taiwan. Aerobic degradation rate constants (k₁) and half-lives (t_1/2) for TBBPA (50 μg g⁻¹) ranged from 0.053 to 0.077 d⁻¹ and 9.0 to 13.1 d, respectively. The degradation of TBBPA (50 μg g⁻¹) was enhanced by adding yeast extract (5 mg L⁻¹), sodium chloride (10 ppt), cellulose (0.96 mg L⁻¹), humic acid (0.5 g L⁻¹), brij 30 (55 μM), brij 35 (91 μM), rhamnolipid (130 mg L⁻¹), or surfactin (43 mg L⁻¹), with rhamnolipid yielding a higher TBBPA degradation than the other additives. For different toxic chemicals in the sediment, the results showed the high-to-low order of degradation rates were bisphenol-A (BPA) (50 μg g⁻¹) > nonylphenol (NP) (50 μg g⁻¹) > 4,4′-dibrominated diphenyl ether (BDE-15) (50 μg g⁻¹) > TBBPA (50 μg g⁻¹) > 2,2′,3,3′,4,4′,5,5′,6,6′-decabromodiphenyl ether (BDE-209) (50 μg g⁻¹). The addition of various treatments changed the microbial community in river sediments. The results also showed that Bacillus pumilus and Rhodococcus ruber were the dominant bacteria in the process of TBBPA degradation in the river sediments.     

Photolytic degradation of decabromodiphenyl ethane (DBDPE)

The photolytic degradation of decabromodiphenyl ethane (DBDPE), an alternative flame retardant to decabromodiphenyl ether, was investigated in a variety of matrixes (n-hexane, tetrahydrofuran, methanol/water, humic acid/water, and silica gel) by irradiation under ultraviolet light and in n-hexane under natural light. Photolytic degradation of DBDPE occurs in all the matrixes investigated within the irradiation period (<320 min). The degradation experiments showed varied reaction rates, dependent on the matrixes, with increasing half-lives (t_1/2) in the order of tetrahydrofuran (t_1/2 = 6.0 min) > n-hexane (t_1/2 = 16.6 min) > humic acid/water (30 < t_1/2 < 60) > silica gel (t_1/2 = 75.9 min) > methanol/water (t_1/2 > 240 min). The reaction in tetrahydrofuran, n-hexane, and silica gel matrixes can be described by the pseudo first order kinetics. Nevertheless, the matrixes have little effect on the degradation product distributions of DBDPE. A numbers of debrominated intermediates were identified. The degradation involves the initial formation of nona-BDPEs and the subsequent decomposition of these congeners to lower brominated congeners (octa- and hepta-BDPEs) within the irradiation time. To our knowledge, the present work is the first attempt to investigate the photolytic degradation kinetics and the identification of intermediates, as well as the degradation mechanism, during the degradation of DBDPE. Further research is needed to understand the photolytic degradation pattern of DBDPE in the natural environment.     

Bioconcentration of ibuprofen in fathead minnow (Pimephales promelas) and channel catfish (Ictalurus punctatus)

Pharmaceutical products and their metabolites are being widely detected in aquatic environments and there is a growing interest in assessing potential risks of these substances to fish and other non-target species. Ibuprofen is one of the most commonly used analgesic drugs and no peer-reviewed laboratory studies have evaluated the tissue specific bioconcentration of ibuprofen in fish. In the current study, fathead minnow (Pimephales promelas) were exposed to 250 μg L⁻¹ ibuprofen for 28 d followed by a 14 d depuration phase. In a minimized bioconcentration test design, channel catfish (Ictalurus punctatus) were exposed to 250 μg L⁻¹ for a week and allowed to depurate for 7 d. Tissues were collected during uptake and depuration phases of each test and the corresponding proportional and kinetic bioconcentration factors (BCFs) were estimated. The results indicated that the BCF levels were very low (0.08-1.4) implying the lack of bioconcentration potential for ibuprofen in the two species. The highest accumulation of ibuprofen was observed in the catfish plasma as opposed to individual tissues. The minimized test design yielded similar bioconcentration results as those of the standard test and has potential for its use in screening approaches for pharmaceuticals and other classes of chemicals.     

Photolytic and photocatalytic degradation of 6-chloronicotinic acid

This work describes for the first time the photolytic and photocatalytic degradation of 6-chloronicotinic acid (6CNA) in double deionised water, which is a degradation product of neonicotinoid insecticides imidacloprid and acetamiprid, and it is known to appear in different environmental matrices. Photolytic experiments were performed with three UVA (ultraviolet A) polychromatic fluorescent lamps with broad maximum at 355 nm, while photocatalytic experiments were performed using immobilised titanium dioxide (TiO₂) on six glass slides in the spinning basket inside a photocatalytic quartz cell under similar irradiation conditions. Photolytic degradation revealed no change in concentration of 6CNA within 120 min of irradiation, while the photocatalytic degradation within 120 min, obeyed first-order kinetics. The observed disappearance rate constant was k = 0.011 ± 0.001 min⁻¹ and t_1/2 was 63.1 ± 5.5 min. Mineralisation rate was estimated through total organic carbon (TOC) and measurements revealed no carbon removal in case of photolysis after 120 min of exposure. However in photocatalytic experiments 46 ± 7% mineralisation was achieved within 120 min of irradiation. Nevertheless, the removal of total nitrogen (TN) was not observed across all experiments. Ion chromatographic analyses indicated transformation of chlorine atoms to chloride and increase of nitrate(V) ions only via photocatalytic experiments. Efficiency of selected advanced oxidation process (AOP) was investigated through toxicity assessment with Vibrio fischeri luminescent bacteria and revealed higher adverse effects of treated samples on bacteria following photocatalytic degradation in spite of the fact that higher mineralisation was achieved. New hydroxylated product generated in photocatalytic experiments with TiO₂, was confirmed with liquid chromatography-electro spray ionisation mass spectrometry (LC-ESI-MS/MS) analyses, gas chromatography-mass spectrometry (GC-MS) and nuclear magnetic resonance spectroscopy (¹H NMR).     

Degradation of paracetamol by advance oxidation processes using modified reticulated vitreous carbon electrodes with TiO2 and CuO/TiO2/Al2O3

The degradation of paracetamol in aqueous solutions in the presence of hydrogen peroxide was carried out by photochemistry, electrolysis and photoelectrolysis using modified 100 pores per inch reticulated vitreous carbon electrodes. The electrodes were coated with catalysts such as TiO₂ and CuO/TiO₂/Al₂O₃ by electrophoresis followed by heat treatment. The results of the electrolysis with bare reticulated vitreous carbon electrodes show that 90% paracetamol degradation occurs in 4 h at 1.3 V vs. SCE, forming intermediates such as benzoquinone and carboxylic acids followed by their complete mineralisation. When the electrolysis was carried out with the modified electrodes such as TiO₂/RVC, 90% degradation was achieved in 2 h while with CuO/TiO₂/Al₂O₃/RVC, 98% degradation took only 1 h. The degradation was also carried out in the presence of UV reaching 95% degradation with TiO₂/RVC/UV and 99% with CuO/TiO₂/Al₂O₃/RVC/UV in 1 h. The reactions were followed by spectroscopy UV-Vis, HPLC and total organic carbon analysis. These studies show that the degradation of paracetamol follows a pseudo-first order reaction kinetics.     

Responses of Hyalella azteca and phytoplankton to a simulated agricultural runoff event in a managed backwater wetland

We assessed the aqueous toxicity mitigation capacity of a hydrologically managed floodplain wetland following a synthetic runoff event amended with a mixture of sediments, nutrients (nitrogen and phosphorus), and pesticides (atrazine, S-metolachlor, and permethrin) using 48-h Hyalella azteca survival and phytoplankton pigment, chlorophyll a. The runoff event simulated a 1 h, 1.27 cm rainfall event from a 16 ha agricultural field. Water (1 L) was collected every 30 min within the first 4 h, every 4 h until 48 h, and on days 5, 7, 14, 21, and 28 post-amendment at distances of 0, 10, 40, 300 and 500 m from the amendment point for chlorophyll a, suspended sediment, nutrient, and pesticide analyses. H. azteca 48-h laboratory survival was assessed in water collected at each site at 0, 4, 24, 48 h, 5 d and 7 d. Greatest sediment, nutrient, and pesticide concentrations occurred within 3 h of amendment at 0 m, 10 m, 40 m, and 300 m downstream. Sediments and nutrients showed little variation at 500 m whereas pesticides peaked within 48 h but at <15% of upstream peak concentrations. After 28 d, all mixture components were near or below pre-amendment concentrations. H. azteca survival significantly decreased within 48 h of amendment up to 300 m in association with permethrin concentrations. Chlorophyll a decreased within the first 24 h of amendment up to 40 m primarily in conjunction with herbicide concentrations. Variations in chlorophyll a at 300 and 500 m were associated with nutrients. Managed floodplain wetlands can rapidly and effectively trap and process agricultural runoff during moderate rainfall events, mitigating impacts to aquatic invertebrates and algae in receiving aquatic systems.     

Biosorption of thorium on the external shell surface of bivalve mollusks: the role of shell surface microtopography

External shell surface (ESS) of bivalve mollusks is known to adsorb various metals dissolved in ambient water in high concentration. It is hypothesized here that the surface microtopography of the thin organic coating layer, periostracum, or calcareous shell (if periostracum was destroyed) plays a major role in the adsorption of actinides on ESS. Thorium (natural alpha-emitter) was used in short-term biosorption experiment with shell fragments of five bivalve mollusks. After a 72 h exposure to Th (∼6 kBq L⁻¹), thorium concentration was measured on ESS using laser ablation inductively coupled plasma mass spectrometry; the distribution and density of alpha tracks were subsequently visualized by α-track autoradiography. A trend in reduced Th concentrations on the ESS was observed depending upon the species tested: (group 1 ∼4000 μg g⁻¹) Chlamys islandica (M.), Mercenaria mercenaria (L.), Dreissena polymorpha (P.) > (group 2 ∼1200 μg g⁻¹) Crassostrea virginica (G.) ? (group 3 ∼150 μg g⁻¹) Mytilus edulis L. The microtopography of ESS was characterized by scanning electron microscopy revealing the high porosity of the calcareous surface of C. islandica and M. mercenaria, lamellate surface of periostracum in D. polymorpha, uneven but a weakly porous surface of periostracum of C. virginica, and a nearly smooth surface of the periostracum of M. edulis. This work has demonstrated, for the first time, the presence of a strong correlation between concentration of adsorbed Th and ESS microtopography, and the role of the periostracum in this process is discussed.     

Zero valent iron mediated degradation of the pharmaceutical diazepam

Parameters that influence the zero valent iron mediated degradation of the pharmaceutical diazepam (DZP) were evaluated including the iron concentration and its pre-treatment, the effect of complexation with EDTA and oxic versus anoxic condition. It was observed that acid pre-treatment of iron particles is important for degradation efficiency and that H₂SO₄ is a better choice than HCl, resulting in higher degradation of DZP. Under oxic conditions, the degradation of DZP achieved 96% after 60 min using Fe⁰ (25 g L⁻¹) pre-treated with H₂SO₄ in the presence of EDTA (119 mg L⁻¹), while mineralization achieved around 60% after the same time. Under anoxic conditions, degradation occurred, however at lower extent, achieving 67% after 120 min. The addition of EDTA improved the treatment efficiency in 20% leading to 99% DZP degradation after 120 min. The first intermediates formed during DZP degradation were identified using LC/MS analysis and revealed the formation of mono- and di-hydroxylated products from DZP during Fe⁰/EDTA/O₂ degradation, which evidences that OH was the main oxidizing species formed in this process.     

Fates and transport of PPCPs in soil receiving reclaimed water irrigation

Fates and transport of 9 commonly found PPCPs of the reclaimed water were simulated based on the HYDRUS-1D software that was validated with data generated from field experiments. Under the default scenario in which the model parameters and input data represented the typical conditions of turf grass irrigation in southern California, the adsorption, degradation, and volatilization of clofibric acid, ibuprofen, 4-tert-octylphenol, 4-n-nonylphenol, naproxen, triclosan, diclofenac sodium, bisphenol A and estrone in the receiving soils were tracked for 10 years. At the end, their accumulations in the 90 cm soil profile varied from less than 1 ng g⁻¹ to about 140 ng g⁻¹ and their concentrations in the drainage water in the 90 cm soil depth varied from nil to μg L⁻¹ levels. The adsorption and microbial degradation processes interacted to contain the PPCPs entirely within surface 40 cm of the soil profiles. Leaching and volatilization were not significant processes governing the PPCPs in the soils. The extent of accumulations in the soils did not appear to produce undue ecological risks to the soil biota. PPCPs did not represent any potential environmental harm in reclaimed water irrigation.     

Enhanced nitrogen deposition exacerbates the negative effect of increasing background ozone in Dactylis glomerata, but not Ranunculus acris

The combined impacts of simulated increased nitrogen (N) deposition (75 kg N ha⁻¹ yr⁻¹) and increasing background ozone (O₃) were studied using two mesotrophic grassland species (Dactylis glomerata and Ranunculus acris) in solardomes, by means of eight O₃ treatments ranging from 15.5 ppb to 92.7 ppb (24 h average mean). A-C_i curves were constructed for each species to gauge effects on photosynthetic efficiency and capacity, and effects on biomass partitioning were determined after 14 weeks. Increasing the background concentration of O₃ reduced the healthy above ground and root biomass of both species, and increased senesced biomass. N fertilisation increased biomass production in D. glomerata, and a significantly greater than additive effect of O₃ and N on root biomass was evident. In contrast, R. acris biomass was not affected by high N. The study shows the combined effects of these pollutants have differential implications for carbon allocation patterns in common grassland species.     

Phototransformation of ibuprofen and ketoprofen in aqueous solutions

The UV (254 nm) and UV/VUV (254/185 nm) photolysis of two anti-inflammatory drugs, ibuprofen and ketoprofen, have been studied in aqueous solutions as a possible process for the removal of non-biodegradable compounds.We have examined the effects of dissolved oxygen and initial target concentration. Upon irradiation at 254 nm, the decomposition rate of ketoprofen is almost forty times higher as it of ibuprofen whilst VUV irradiation only increased the ibuprofen decomposition rate. The presence of dissolved oxygen accelerated the photodegradation of ibuprofen, whereas no effect was observed on the degradation of ketoprofen. The maximum quantum yield for the phototransformation was 0.2. The rate of mineralization in both cases was ∼60%, even after 1 h of treatment and this suggests the formation of stable by-products which were identified using GC-MS and HPLC-MS, respectively.     

Photocatalytic degradation of five sulfonylurea herbicides in aqueous semiconductor suspensions under natural sunlight

In the present study, the photocatalytic degradation of five sulfonylurea herbicides (chlorsulfuron, flazasulfuron, nicosulfuron, sulfosulfuron and triasulfuron) has been investigated in aqueous suspensions of zinc oxide (ZnO), tungsten (VI) oxide (WO₃), tin (IV) oxide (SnO₂) and zinc sulfide (ZnS) at pilot plant scale under natural sunlight. Photocatalytic experiments, especially those involving ZnO photocatalysis, showed that the addition of semiconductors in tandem with the oxidant (Na₂S₂O₈) strongly enhances the degradation rate of the herbicides in comparisons carried out with photolytic tests. The degradation of the herbicides follows a first order kinetics according to the Langmuir-Hinshelwood model. In our conditions, the amount of time required for 50% of the initial pesticide concentration to dissipate (t_½) ranged from 8 to 27 min (t_30W = 0.3-1.2 min) for sulfosulfuron and chlorsulfuron, respectively in the ZnO/Na₂S₂O₈ system. None of the studied herbicides was found after 120 min of illumination (except chlorsulfuron, 0.2 μg L⁻¹).     

Enzymatic and microbial transformation assays for the evaluation of the environmental fate of diclofenac and its metabolites

Diclofenac has been of environmental concern due to the potential harmful effects on non-target organisms at environmentally relevant concentrations. In this study, we evaluated the transformation kinetics of diclofenac and its two major metabolites in two laboratory-scale experiments: the transformation of diclofenac in the presence of rat liver S9 fraction with co-factors, and the transformation of diclofenac, 4′-hydroxy-diclofenac and diclofenac β-O-acyl glucuronide in the inoculum used for the OECD 301C ready-biodegradability test. 4′-Hydroxy-diclofenac was identified as the major phase I metabolite and diclofenac β-O-acyl glucuronide was identified as the major phase II metabolite in the S9 assay. Transformation of diclofenac in the microbial degradation test did not occur significantly for 28 d, whereas 4′-hydroxy-diclofenac degraded slowly, indicating that the biological removal of diclofenac is not likely to occur in conventional STPs unless sorptive removal is significant. However, diclofenac β-O-acyl glucuronide deconjugated to form equimolar diclofenac within 7 d, in the microbial degradation test. The mixture of diclofenac and its two metabolites, formed after incubating diclofenac in S9 medium for 2 h, was spiked in the inoculum to link both assays. The concentrations of diclofenac and its metabolites, measured over time, agreed well with predicted values, using rate parameters obtained from independent experiments. The results show that phase II metabolites generated in mammals may deconjugate easily in conventional STPs to form a parent compound and that these processes should be considered during the environmental monitoring and risk assessment of diclofenac.     

Photocatalytic degradation with immobilised TiO(2) of three selected neonicotinoid insecticides: imidacloprid, thiamethoxam and clothianidin

This research focused on photocatalytic degradation of imidacloprid, thiamethoxam and clothianidin employing a tailor-made photoreactor with six polychromatic fluorescent UVA (broad maximum at 355 nm) lamps and immobilised titanium dioxide (TiO₂) on glass slides. The disappearance was followed by high pressure liquid chromatography (HPLC-DAD) analyses, wherein the efficiency of mineralization was monitored by measurements of total organic carbon (TOC). Within 2 h of photocatalysis, all three neonicotinoids were degraded following first order kinetics with rate constants k = 0.035 ± 0.001 min⁻¹ for imidacloprid, k = 0.019 ± 0.001 min⁻¹ for thiamethoxam and k = 0.021 ± 0.000 min⁻¹ for clothianidin. However, the rate of mineralization was low, i.e. 19.1 ± 0.2% for imidacloprid, 14.4 ± 2.9% for thiamethoxam and 14.1 ± 0.4% for clothianidin. This indicates that several transformation products were formed instead. Some of them were observed within HPLC-DAD analyses and structures were proposed according to the liquid chromatography-electro spray ionization tandem mass spectrometry analyses (LC-ESI-MS/MS). The formation of clothianidin, as thiamethoxam transformation product, was reported for the first time.