Fate of citalopram during water treatment with O3, ClO2, UV and Fenton oxidation

In the present study we investigate the fate of citalopram (CIT) at neutral pH using advanced water treatment technologies that include O₃, ClO₂ oxidation, UV irradiation and Fenton oxidation. The ozonation resulted in 80% reduction after 30 min treatment. Oxidation with ClO₂ removed >90% CIT at a dosage of 0.1 mg L⁻¹. During UV irradiation 85% reduction was achieved after 5 min, while Fenton with addition of 14 mg L⁻¹ (Fe²⁺) resulted in 90% reduction of CIT. During these treatment experiments transformation products (TPs) were formed from CIT, where five compounds were identified by using high resolution and tandem mass spectrometry. Among these desmethyl-citalopram and citalopram N-oxide have been previously identified as human metabolites, while three are novel and published here for the first time. The three TPs are a hydroxylated dimethylamino-side chain derivative, a butyrolactone derivative and a defluorinated derivative of CIT.     

Parathion degradation and its intermediate formation by Fenton process in neutral environment

The purpose of this study is to investigate parathion degradation by Fenton process in neutral environment. The initial parathion concentration for all the degradation experiments was 20 ppm. For hydrogen ion effect on Fenton degradation, the pH varied from 2 to 8 at the [H₂O₂] to [Fe²⁺] ratio of 2-2 mM, and the result showed pH 3 as the most effective environment for parathion degradation by Fenton process. Apparent degradation was also observed at pH 7. The subsequent analysis for parathion degradation was conducted at pH 7 because most environmental parathion exists in the neutral environment. Comparing the parathion degradation results at various Fenton dosages revealed that at Fe²⁺ concentrations of 0.5, 1.0 and 1.5 mM, the Fenton reagent ratio ([H₂O₂]/[Fe²⁺]) for best-removing performance were found as 4, 3, and 2, resulting in the removal efficiencies of 19%, 48% and 36%, respectively. Further increase in Fe²⁺ concentration did not cause any increase of the optimum Fenton reagent ratio for the best parathion removal. The result from LC-MS also indicated that hydroxyl radicals might attack the PS double bond, the single bonds connecting nitro-group, nitrophenol, or the single bond within ethyl groups of parathion molecules forming paraoxons, nitrophenols, nitrate/nitrite, thiophosphates, and other smaller molecules. Lastly, the parathion degradation by Fenton process at the presence of humic acids was investigated, and the results showed that the presence of 10 mg L⁻¹ of humic acids in the aqueous solution enhanced the parathion removal by Fenton process twice as much as that without the presence of humic acids.     

Removal of Rhodamine B under visible irradiation in the presence of Fe⁰, H₂O₂, citrate and aeration at circumneutral pH

A new Vis-Fe⁰-H₂O₂-citrate-O₂ system comprising zero-valent iron, hydrogen peroxide, citrate anion and aeration at circumneutral pH under visible irradiation was studied. 21 μmol L⁻¹ of Rhodamine B (RhB) was chosen as the substrate to be tested. Experiments were conducted under conditions of 2.9 mmol L⁻¹ of H₂O₂, 12.6 g of Fe⁰ and 1.0 mmol L⁻¹ of citrate at pH 7.5. Results showed that, in 1 h reaction, 54% of RhB was removed with corresponding 26% of COD reduced. Meanwhile, the amount of released dissolved irons from Fe⁰ surface was found to be at a very low level as <5.4 μmol L⁻¹. Extinguishing tests with isopropanol suggested that RhB oxidation by hydroxyl radicals was the main process taken place in Vis-Fe⁰-H₂O₂-citrate-O₂ system, which accounted for 75% of substrate removal in 3 h reaction. Control and factor influencing experiments showed that the prohibitive extents of individual factor importance on RhB removal followed a decreasing order of Fe⁰ > H₂O₂ > citrate > Vis > O₂. This study showed an excellent system that could remove refractory organic compounds from water in laboratory researches, and also provided a good idea to reduce secondary contamination by dissolved irons in future investigations.     

Nitrogen leaching and acidification during 19 years of NH₄NO₃ additions to a coniferous-forested catchment at Gårdsjön, Sweden (NITREX)

The role of nitrogen (N) in acidification of soil and water has become relatively more important as the deposition of sulphur has decreased. Starting in 1991, we have conducted a whole-catchment experiment with N addition at Gårdsjön, Sweden, to investigate the risk of N saturation. We have added 41 kg N ha⁻¹ yr⁻¹ as NH₄NO₃ to the ambient 9 kg N ha⁻¹ yr⁻¹ in fortnightly doses by means of sprinkling system. The fraction of input N lost to runoff has increased from 0% to 10%. Increased concentrations of NO₃ in runoff partially offset the decreasing concentrations of SO₄ and slowed ecosystem recovery from acid deposition. From 1990-2002, about 5% of the total N input went to runoff, 44% to biomass, and the remaining 51% to soil. The soil N pool increased by 5%. N deposition enhanced carbon (C) sequestration at a mean C/N ratio of 42-59 g g⁻¹.     

Denitrification of synthetic concentrated nitrate wastes by aerobic granular sludge under anoxic conditions

The aim of the present work was to determine the denitrification potential of aerobic granular sludge for concentrated nitrate wastes. We cultivated mixed microbial granules in a sequencing batch reactor operated at a superficial air velocity of 0.8 cm s⁻¹. The denitrification experiments were performed under anoxic conditions using serum bottles containing synthetic media with 225-2250 mg L⁻¹ NO₃-N. Time required for complete denitrification varied with the initial nitrate concentration and acetate to nitrate-N mass ratio. Complete denitrification of 2250 mg L⁻¹ NO₃-N under anoxic conditions was accomplished in 120 h. Nitrite accumulation was not significant (<5 mg N L⁻¹) at initial NO₃-N concentrations below 677 mg L⁻¹. However, denitrification of higher concentrations of nitrate (?900 mg N L⁻¹) resulted in buildup of nitrite. Nevertheless, nitrite buildups observed in present study were relatively lower compared to that reported in previous studies using flocculent activated sludge. The experimental results suggest that acetate-fed aerobic granular sludge can be quickly adapted to treat high strength nitrate waste and can thus be used as seed biomass for developing high-rate bioreactors for efficient treatment of concentrated nitrate-bearing wastes.     

Susceptibility of epigeic earthworm Eisenia fetida to agricultural application of six insecticides

Ecotoxicological risks of agricultural application of six insecticides to soil organisms were evaluated by acute toxicity tests under laboratory condition following OECD guidelines using the epigeic earthworm Eisenia fetida as the test organism. The organochlorine insecticide endosulfan (LC₅₀ - 0.002 mg kg⁻¹) and the carbamate insecticides aldicarb (LC₅₀ - 9.42 mg kg⁻¹) and carbaryl (LC₅₀ - 14.81 mg kg⁻¹) were found ecologically most dangerous because LC₅₀ values of these insecticides were lower than the respective recommended agricultural dose (RAD). Although E. fetida was found highly susceptible to the pyrethroid insecticide cypermethrin (LC₅₀ - 0.054 mg kg⁻¹), the value was higher than its RAD. The organophosphate insecticides chlorpyrifos (LC₅₀ - 28.58 mg kg⁻¹), and monocrotophos (LC₅₀ - 39.75 mg kg⁻¹) were found less toxic and ecologically safe because the LC₅₀ values were much higher than their respective RAD.     

Satellite derived trends in NO2 over the major global hotspot regions during the past decade and their inter-comparison

We assessed satellite derived tropospheric NO₂ distribution on a global scale and identified the major NO₂ hotspot regions. Combined GOME and SCIAMACHY measurements for the period 1996-2006 have been used to compute the trends over these regions. Our analysis shows that tropospheric NO₂ column amounts have increased over the newly and rapidly developing regions like China (11 ± 2.6%/year), south Asia (1.76 ± 1.1%/year), Middle East (2.3 ± 1%/year) and South Africa (2.4 ± 2.2%/year). Tropospheric NO₂ column amounts show some decrease over the eastern US (−2 ± 1.5%/year) and Europe (0.9 ± 2.1%/year). We found that although tropospheric NO₂ column amounts decreased over the major developed regions in the past decade, the present tropospheric NO₂ column amounts over these regions are still significantly higher than those observed over newly and rapidly developing regions (except China). Tropospheric NO₂ column amounts show some decrease over South America and Central Africa, which are major biomass burning regions in the Southern Hemisphere.     

Nitrous oxide and methane emission from a flooded rice field as influenced by separate and combined application of herbicides bensulfuron methyl and pretilachlor

Combination of divergent active principles to achieve broad-spectrum control is gaining popularity to manage the weed menace in intensive agriculture. However, such application could have non-target impacts on the soil processes affecting soil ecology and environmental interactions. A field experiment was conducted to investigate the impact of separate and combined applications of herbicides bensulfuron methyl and pretilachlor on the emission of N₂O and CH₄, and related soil and microbial parameters in a flooded alluvial field planted to rice cv Lalat. Single application of the herbicide bensulfuron methyl or pretilachlor resulted in a significant reduction of N₂O and CH₄ emissions while the combination of these two herbicides distinctly increased N₂O and CH₄ emissions. Cumulative N₂O emissions (kg N₂O-N) followed the order of bensulfuron methyl (0.35 kg ha⁻¹) < pretilachlor (0.36 kg ha⁻¹) < control (0.45 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (0.49 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (0.54 kg ha⁻¹). Cumulative CH₄ emissions (kg CH₄), on the other hand, followed the order of bensulfuron methyl (47.89 kg ha⁻¹) < pretilachlor (73.17 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% single dose (93.50 kg ha⁻¹) < control (106.54 kg ha⁻¹) < bensulfuron methyl 0.6% + pretilachlor 6.0% double dose (124.67 kg ha⁻¹). The inhibitory effect of separate application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% on N₂O emission was linked to lower mineral N, lower denitrifying and nitrifying activity and low denitrifier and nitrifier populations. Inhibitory effect on CH₄ emission, on the contrary, was linked to prevention in the drop of redox potential, lower readily mineralizable carbon (RMC) and microbial biomass carbon (MBC) contents as well as lower methanogenic and higher methanotrophic bacterial population. Admittedly, stimulatory effect of combined application of herbicides bensulfuron methyl 0.6% and pretilachlor 6.0% at double dose on N₂O and CH₄ emission was related to reversal of the identified indicators of inhibition. Results indicate that while individual application of herbicides bensulfuron methyl 0.6% or pretilachlor 6.0% can reduce N₂O and CH₄ emission from flooded soil planted to rice, their combined application at normal dose can keep the emission at a comparatively lower level with significantly higher grain yield as compared to the herbicides applied alone.     

The short-term effects of air pollution on adolescent lung function in Taiwan

A mass screening of lung function associated with air pollutants for children is limited. This study assessed the association between air pollutants exposure and the lung function of junior high school students in a mass screening program in Taipei city, Taiwan. Among 10,396 students with completed asthma screening questionnaires and anthropometric measures, 2919 students aged 12-16 received the spirometry test. Forced vital capacity (FVC) and forced expiratory flow in 1 s (FEV₁) in association with daily ambient concentrations of particulate matter with diameter of 10 μm or less (PM₁₀), sulfur dioxide (SO₂), carbon monoxide (CO), nitrogen dioxide (NO₂), and ozone (O₃) were assessed by regression models controlling for the age, gender, height, weight, student living districts, rainfall and temperature. FVC, had a significant negative association with short-term exposure to O₃ and PM₁₀ measured on the day of spirometry testing. FVC values also were reversely associated with means of SO₂, O₃, NO₂, PM₁₀ and CO exposed 1 d earlier. An increase of 1-ppm CO was associated with the reduction in FVC for 69.8 mL (95% CI: −115, −24.4 mL) or in FEV₁ for 73.7 mL (95% CI: −118, −29.7 mL). An increase in SO₂ for 1 ppb was associated with the reductions in FVC and FEV₁ for 12.9 mL (95% CI: −20.7, −5.09 mL) and 11.7 mL (95% CI: −19.3, −4.16 mL), respectively. In conclusion, the short-term exposure to O₃ and PM₁₀ was associated with reducing FVC and FEV₁. CO and SO₂ exposure had a strong 1-d lag effect on FVC and FEV₁.     

Phosphine migration at the water-air interface in Lake Taihu, China

The diurnal atmospheric phosphine (PH₃) concentrations and fluxes at the water-air interface in Lake Taihu were reported. The results showed that the PH₃ flux at the water-air interface ranged from −69.9 ± 29.7 to 121 ± 42 ng m⁻² h⁻¹, with a mean flux of 14.4 ± 22.5 ng m⁻² h⁻¹. The fluxes were both negative and positive during the diurnal period, indicating that the lake can act as a sink and a source of PH₃. In addition, the PH₃ fluxes were positively correlated with water temperature, total soluble phosphorus and soluble reactive phosphorus, while they were negatively correlated with water redox potential. A similar diurnal variation curve of atmospheric PH₃ concentrations was observed during all four seasons, with the maximum level occurring in early morning and the minimum appearing around midday. These findings suggest that light plays an important role in the elimination of atmospheric PH₃. A significant positive correlation was also found between air temperature and atmospheric PH₃ concentration. The mean flux of PH₃ in Lake Taihu was higher than in other reported wetlands, with an estimated annual emission of PH₃ to the atmosphere of 2.94 × 10⁵ g y⁻¹.     

Effects of previous sublethal pulse to ammonium nitrate on mortality and total length on Epidalea calamita larvae

Ammonium nitrate is one of the most widespread contaminants related with the viability of natural amphibian populations. In this study we have evaluated in terms of mortality and total length the effects that a previous sublethal pulse to ammonium nitrate generates in Epidalea calamita. Experiments were divided in two phases. In the first one, tadpoles were exposed to two different treatments, with and without a low ammonium nitrate concentration (22 mg NH₄NO₃ L⁻¹). The second phase consisted in static toxicity experiments from both origin treatments with five different nominal concentrations (0, 22, 45, 90 and 180 mg NH₄NO₃ L⁻¹). Results showed that tadpoles that had experienced a previous sublethal exposure showed a negative effect on survival (57% of reduction in the LC₅₀ value) and total length, throughout an increase in their sensitivity. These results could help us to understand the situation of amphibian populations inhabiting aquatic ecosystems exposed to discontinuous and variable pulses of pollutants.     

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.     

Nano-TiO2 enhances the toxicity of copper in natural water to Daphnia magna

The acute toxicity of engineered nanoparticles (NPs) in aquatic environments at high concentrations has been well-established. This study demonstrates that, at a concentration generally considered to be safe in the environment, nano-TiO₂ remarkably enhanced the toxicity of copper to Daphnia magna by increasing the copper bioaccumulation. Specifically, at 2 mg L⁻¹ nano-TiO₂, the (LC₅₀) of Cu²⁺ concentration observed to kill half the population, decreased from 111 μg L⁻¹ to 42 μg L⁻¹. Correspondingly, the level of metallothionein decreased from 135 μg g⁻¹ wet weight to 99 μg g⁻¹ wet weight at a Cu²⁺ level of 100 μg L⁻¹. The copper was found to be adsorbed onto the nano-TiO₂, and ingested and accumulated in the animals, thereby causing toxic injury. The nano-TiO₂ may compete for free copper ions with sulfhydryl groups, causing the inhibition of the detoxification by metallothioneins.     

Oxidation of bisphenol F (BPF) by manganese dioxide

Bisphenol F (BPF), an environmental estrogen, is used as a monomer in plastic industry and its environmental fate and decontamination are emerging concern. This study focused on the kinetics, influencing factors and pathways of its oxidation by MnO₂. At pH 5.5, about 90% of BPF was oxidized in 20 min in a solution containing 100 μM MnO₂ and 4.4 μM BPF. The reaction was pH-dependent, following an order of pH 4.5 > pH 5.5 > pH 8.6 > pH 7.5 > pH 6.5 > pH 9.6. Humic acids inhibited the reaction at low (≤pH 5.5) and high pH (≥pH 8.6) at high concentrations. In addition, metal ions and anions also suppressed the reaction, following the order Mn²⁺ > Ca²⁺ > Mg²⁺ > Na⁺ and HPO₄²⁻ > Cl⁻ > NO₃⁻ ≈ SO₄²⁻, respectively. A total of 5 products were identified, from which a tentative pathway was proposed.     

Responses of herbaceous plants to urban air pollution: Effects on growth, phenology and leaf surface characteristics

Vehicle exhaust emissions are a dominant feature of urban environments and are widely believed to have detrimental effects on plants. The effects of diesel exhaust emissions on 12 herbaceous species were studied with respect to growth, flower development, leaf senescence and leaf surface wax characteristics. A diesel generator was used to produce concentrations of nitrogen oxides (NO_x) representative of urban conditions, in solardome chambers. Annual mean NO_x concentrations ranged from 77 nl l^−l to 98 nl l⁻¹, with NO:NO₂ ratios of 1.4-2.2, providing a good experimental simulation of polluted roadside environments. Pollutant exposure resulted in species-specific changes in growth and phenology, with a consistent trend for accelerated senescence and delayed flowering. Leaf surface characteristics were also affected; contact angle measurements indicated changes in surface wax structure following pollutant exposure. The study demonstrated clearly the potential for realistic levels of vehicle exhaust pollution to have direct adverse effects on urban vegetation.     

Atmospheric transport of urban-derived NH(x): Evidence from nitrogen concentration and delta(15)N in epilithic mosses at Guiyang, SW China

Nitrogen concentration and δ¹⁵N in 175 epilithic moss samples were investigated along four directions from urban to rural sites in Guiyang, SW China. The spatial variations of moss N concentration and δ¹⁵N revealed that atmospheric N deposition is dominated by NH_x-N from two major sources (urban sewage NH₃ and agricultural NH₃), the deposition of urban-derived NH_x followed a point source pattern characterized by an exponential decline with distance from the urban center, while the agricultural-derived NH_x was shown to be a non-point source. The relationship between moss N concentration and distance (y = 1.5e^−0.13x + 1.26) indicated that the maximum transporting distance of urban-derived NH_x averaged 41 km from the urban center, and it could be determined from the relationship between moss δ¹⁵N and distance [y = 2.54 ln(x) − 12.227] that urban-derived NH_x was proportionally lower than agricultural-derived NH_x in N deposition at sites beyond 17.2 km from the urban center. Consequently, the variation of urban-derived NH_x with distance from the urban center could be modeled as y = 56.272e^−0.116x − 0.481 in the Guiyang area.     

Using native epiphytic ferns to estimate the atmospheric mercury levels in a small-scale gold mining area of West Java, Indonesia

Mercury pollution is caused by artisanal and small-scale gold mining (ASGM) operations along the Cikaniki River (West Java, Indonesia). The atmosphere is one of the primary media through which mercury can disperse. In this study, atmospheric mercury levels are estimated using the native epiphytic fern Asplenium nidus complex (A. nidus) as a biomonitor; these estimates shed light on the atmospheric dispersion of mercury released during mining.Samples were collected from 8 sites along the Cikaniki Basin during September-November, 2008 and September-November, 2009.The A. nidus fronds that were attached to tree trunks 1-3 m above the ground were collected and measured for total mercury concentration using cold vapor atomic absorption spectrometry (CVAAS) after acid-digestion. The atmospheric mercury was collected using porous gold collectors, and the concentrations were determined using double-amalgam CVAAS.The highest atmospheric mercury concentration, 1.8 × 10³ ± 1.6 × 10³ ng m⁻³, was observed at the mining hot spot, and the lowest concentration of mercury, 5.6 ± 2.0 ng m⁻³, was observed at the remote site from the Cikaniki River in 2009. The mercury concentrations in A. nidus were higher at the mining village (5.4 × 10³ ± 1.6 × 10³ ng g⁻¹) than at the remote site (70 ± 30 ng g⁻¹). The distribution of mercury in A. nidus was similar to that in the atmosphere; a significant correlation was observed between the mercury concentrations in the air and in A. nidus (r = 0.895, P < 0.001, n = 14). The mercury levels in the atmosphere can be estimated from the mercury concentration in A. nidus using a regression equation: log (Hg_A.nidu/ng g⁻¹) = 0.740 log (Hg_Air/ng m⁻³) − 1.324.     

Phenol depletion by thermally activated peroxydisulfate at 70°C

The ability of thermal activated peroxydisulfate (PS) of mineralizing phenol at 70 °C from contaminated waters is investigated. Phenol in concentrations of 10⁻⁴ to 5 × 10⁻⁴ M is quantitatively depleted by 5 × 10⁻³ to 10⁻² M activated PS in 15 min of reaction. However, mineralization of the organic carbon is not observed. Instead, an insoluble phenol polymer-type product is formed. A reaction mechanism including the formation of phenoxyl radicals and validated by computer simulations is proposed. High molecular weight phenolic products are formed by phenoxyl radical H-abstraction reactions. This is not the case for the room temperature degradation of phenol by sulfate radicals where sulfate addition to the aromatic ring mainly leads to the generation of hydroxycyclohexadienyl radicals leading to hydroxybenzenes and oxidized open chain products. Therefore, a change in the reaction mechanism is observed with increasing temperature, and thermal activation of PS at 70 °C does not lead to the mineralization of phenol. Thus PS activation at 70 °C may be considered a potential method to reduce the load of phenol in polluted waters by polymerization.     

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.