Visible-Light-Driven Photocatalytic N-Doped TiO<Subscript>2</Subscript> for Degradation of Bisphenol A (BPA) and Reactive Black 5 (RB5) Dye

Bisphenol A (BPA) and reactive black 5 (RB5) dye are among the most persistent and non-biodegradable contaminants in water which require an urgent need for the development of effective removal method. The ubiquitous existence of both contaminants could interfere with the human health and aquatic environmental balance. Photocatalytic process as one of advanced oxidation processes (AOPs) has shown high performance for degradation of organic compounds to the harmless materials under sensible condition. Therefore, this study aims to develop a visible-light-driven photocatalyst that can efficiently degrade BPA and RB5 present in household water. N-doped TiO₂ were successfully synthesized via simple and direct sol–gel method. The prepared TiO₂ nanoparticles were characterized by field emission scanning microscope (FE-SEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR), and Brunauere Emmette Teller (BET) analysis. The incorporation of nitrogen in TiO₂ lattice exhibited excellent optical responses to visible region as revealed by UV–Vis–NIR spectroscopy absorption capability at 400–600 nm. The photocatalytic activity of the N-doped TiO₂ nanoparticles was measured by photocatalytic degradation of BPA and RB5 in an aqueous solution under visible-light irradiations. Degradation of BPA and RB5 was 91.3% and 89.1%, respectively after 360 min illumination. The degradation of BPA and RB5 by N-doped TiO₂ was increased up to 89.8% and 88.4%, respectively under visible-light irradiation as compared to commercial TiO₂ P25. This finding clearly shows that N-doped TiO₂ exhibits excellent photocatalytic degradation of BPA and RB5 under visible irradiation, hence have a promising potential in removing various recalcitrant contaminants for water treatment to fulfill the public need to consume clean water.

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Remediation of polychlorinated biphenyl-contaminated soil by soil washing and subsequent TiO2 photocatalytic degradation

Purpose

An efficient method was developed for treating polychlorinated biphenyl (PCB)-contaminated soil by soil washing and subsequent TiO₂ photocatalytic degradation, and the photocatalytic degradation mechanism of PCBs was explored.

Materials and methods

Hydroxypropyl-??-cyclodextrin (HP??CD) and polyoxyethylene lauryl ether (Brij35) were used to extract PCBs from contaminated soil at first, and then the degradation of PCBs in the soil extracts was performed by TiO₂ photocatalysis under UV irradiation.

Results and discussion

Washing conditions including washing time, the concentration of HP??CD/Brij35, and the ratio of soil mass to solution volume for extracting 2,4,4??-trichlorobiphenyl (PCB28) from a PCB28-spiked soil were investigated at first. The results indicated that both HP??CD and Brij35 exhibited good performance. The intermediates of photocatalytic degradation of PCB28 were from its dechlorination and hydroxylation in the HPCD and aqueous solutions, respectively. A field PCB-contaminated soil from e-waste recycling sites was treated by this method. The results showed that the extracting percentage was significantly affected by the chlorination degree of PCBs, and HP??CD slowed down the photocatalytic degradation efficiency of overall PCBs.

Conclusions

Soil washing and subsequent TiO₂ photocatalytic degradation was successfully applied for treating PCB-contaminated soil, and HP??CD strongly altered the pathways of the photocatalytic degradation of PCBs.     

Fast and High Amount of Uranyl Ion Uptake by p(Vinyl Phosphonic Acid) Microgels Prepared by UV Irradiation Technique

Micrometer-size poly(vinyl phosphonic acid) (p(VPA)) hydrogel was synthesized by employing UV irradiation of an emulsion containing vinyl phosphonic acid (VPA) and crosslinker, prepared using lecithin as surfactant and gasoline as solvent. The p(VPA) microgels were employed in absorption of UO₂ ²⁺ ions from aqueous environments and have very high and fast absorption capacity. In about 20 min, 670 mg UO₂ ²⁺ ions were absorbed per gram of p(VPA) microgel from the prepared UO₂ ²⁺ ion solution, and the absorption capacity increased up to 900 mg at pH 6. Various parameters affecting UO₂ ²⁺ absorption characteristics of p(VPA) were investigated. It was found that the Langmuir isotherm fitted the absorption characteristics of p(VPA) better than the Freundlich isotherm. Moreover, magnetic ferrite can be prepared within p(VPA) and used as a magnetically responsive p(VPA) microgel composite for externally controlled absorption of UO₂ ²⁺ ions with little decrease in the absorption capacity of the p(VPA) microgel.

Degradation of Hazardous Dyes in Wastewater using Nanometer Mixed Crystal TiO2 Powders under Visible Light Irradiation

The partial phase transformation of nanometer TiO₂ powder from anatase phase to rutile phase was realized by heat-treatment and a new TiO₂ photocatalyst which could be excited by visible light was obtained. The heat-treated TiO₂ powder at different stage of transition crystal was characterized and monitored by XRD, TEM, FT-IR and UV–vis DRS methods. The test of photocatalytic activity of the heat-treated TiO₂ powder was carried out by the photocatalytic degradation of rhodamine B and acid orange II dyes, respectively, in aqueous solution under visible light irradiation. The results indicate that the nanometer TiO₂ photocatalyst heat-treated at 500°C for 60 min shows the highest photocatalytic activity, that is, it can effectively degrade the rhodamine B and acid orange II under visible light irradiation. The remarkable improvement of photocatalytic activity of heat-treated TiO₂ powder at 500°C for 60 min was mainly illustrated by the formation of special interphase between rutile and anatase phases, which not only restrains the recombination of photogenerated electrons and holes, but also reduces the adsorbability of nanometer anatase TiO₂ powder properly for various dyes. Additionally, the effects of dye-assisting chemicals such as Na₂CO₃ and NaCl on the photocatalytic degradation were also studied.     

TiO2 photocatalytic degradation of tetracycline as affected by a series of environmental factors

Purpose

TiO₂ photocatalytic degradation of tetracycline (TC) in aqueous solution under UV irradiation was investigated as affected by different environmental factors, including cations, anions, organic acids, and surfactants.

Materials and methods

The solution of TC with TiO₂ was irradiated by medium mercury lamp. The concentrations of TC and metal ions were analyzed by HPLC and AAS, respectively. The degradation efficiency of TC was calculated based on TC disappearance.

Results and discussion

Photocatalysis was very effective for TC removal. The degradation efficiency of TC was significantly enhanced in the presence of Cu²⁺/Pb²⁺, SO₄ ^2?/Cl^?, and humic acid (HA) in the examined range, but did no change with Ni²⁺, Cd²⁺, or Zn²⁺. In addition, the results also showed that solution Cu²⁺ and Pb²⁺ ions could be reduced during the process, while Ni²⁺, Cd²⁺, and Zn²⁺ were still kept in the solution. However, tannic acid (TA), gallic acid (GA), citric acid (CA), salicylic acid (SA), hydroxypropyl-β-cyclodextrin (HPCD), polyoxyethylene lauryl ether (Brij35), or polyoxyethylenesorbitan monooleate (Tween80) significantly decreased the degradation efficiency of TC.

Conclusions

The photocatalytic approach could be successfully applied to remove TC, and environmental factors significantly influenced its degradation efficiency. It would be useful to understand the environmental behaviors of TC and for the implementation of remediation strategies of TC.     

Community Refinery Wastewater Photodegradation by Fe-Doped TiO<Subscript>2</Subscript> Films

Photocatalytic treatment of real community wastewater using Fe-doped TiO₂ nanofilm was prepared by modified sol-gel method together with a simple dip-coating technique. The process was investigated in a home-made batch photoreactor. The as-prepared nanocomposite film was characterized by UV-Vis diffuse, XRD, BET, and Fe-SEM analysis. The poultry processing wastewater was collected from Nakhonsawan Municipality. Subsequently, the photocatalytic treatment of the wastewater was performed using a home-made photoreactor operated in batch mode to demonstrate the effects of Fe-dopant concentration with various layer numbers. The catalysts were irradiated using four lamps of 15 W power that emitted visible light and performed at room temperature. The samples were collected every 15 min and analyzed for biochemical oxygen demand (BOD) and chemical oxygen demand (COD) removal efficiency compared to pure TiO₂ nanofilm and direct photolysis. From the results, the mixture of rutile and anatase was obtained with the maximum specific surface area of 150.12 mg²/g and the average particle size of 39.95 nm for 3 layers of 0.15% wt/v Fe-doped TiO₂. The BOD and COD value at 90 min time treatment was presented to be 8.87 and 32 mg L^?1, respectively, in the presence of 0.15% wt/v Fe-doped TiO₂ film photocatalysts. Moreover, atomic absorption spectrometric result ensured that no Ti contamination was detected in all parts of plants after watering by the treated water. Hence, the photocatalytic treatment markedly improved the quality of the community wastewater.     

Mercury antagonists: Effects of sodium chloride and sulfur group (VIa) compounds on excystment of the brine shrimp artemia

Brine shrimp excystment, although highly resistant, is severely inhibited by mmolar mercuric chloride. The presence of 100 mmolar NaCl largely prevents the toxic response. The chloride effect can be explained if the toxic Hg species, neutral HgCl₂, is converted into HgCl _inf3 ^sup2? and HgCl _inf4 ^sup2? since charged species not likely to penetrate cyst walls. Other Hg antagonists include SO _in3 ^su2? , SeO _inf3 ^sup2? , TeO _inf3 ^sup2? and TeO _inf4 ^sup2? , but not SO _inf4 ^sup2? and SeO _inf4 ^sup2? . The activity of both Te species can be explained by ready reduction of Te(VI) to Te(IV). Significant anti-mercurial effects were seen in mmolar thiols, ethionine and organoselenium compounds. Thiamine and methionine were both active Hg antagonists at 10 to 30 mmolar levels. The activities of S, Se and Cl^? compounds show that both geochemical and physiological modes of defense against and adaptation to high Hg levels exist.     

Intercomparison of snow Sampling and Analysis Within the Alpine-Wide Snowpack Investigation (SNOSP)

In order to investigate the seasonal and geographical distribution of snow concentrations anddeposition fluxes of environmentally relevant ionic species in the Alps, the international programSNOSP was initiated. In the framework of this program, intercomparisons of snow samplingtechniques and analytical methods to determine the ionic species C1^-, NO ₃ ^- ,SO ₄ ^2- , K⁺, Na⁺, NH4 ⁺, Mg²⁺, and Ca²⁺, as well as the pH and the specificconductivity were performed. The concentrations of these species in the snow samples collectedin the SNOSP program varied by orders of magnitude with, e.g., concentrations of NO ₃ ^- , SO ₄ ^2- , and NH4 ⁺ ranging from 0.2-60, 0.2-90, and 0.1-60 µeq L^-1,respectively. The intercomparisons revealed a reasonable agreement of the determinations of thespecies Cl^-, NO ₃ ^- , SO ₄ ^2- , Na⁺, and NH4 ⁺ in snow. Results were less satisfactory for K⁺, Mg²⁺, Ca²⁺,and H⁺, mainly due to the very low concentrations. In conclusion, recommendations areformulated for the reliable derivation of chemical inventories from snow packs.     

Effects of oxalic acid and lime on the enchytraeid Cognettia sphagnetorum (VEJD) in mor humus

A two-factor orthogonal plan of experimental design was used to estimate a coupled influence of oxalic acid and lime on the enchytraeid Cognettia sphagnetorum in mor humus. Calcium carbonate (X ₁ ) in doses of 0, 300 and 600 mg per 10 g dry wt of mor humus and oxalic acid (X ₂ ) in doses of 0, 45 and 90 mg were added in accordance with the plan. Enchytraeid number (initial number — 50 per container) after three weeks of experiment was maximal at the medium calcium carbonate dose and absence of oxalic acid and minimal at the highest doses of the compounds. Influence of the compounds on the enchytraeid number (Y) is described by the second order equations: $$Y = 23.4 - 3.3X_1 - 6.8X_2 - 3.4X_1 X_2 - 7.7X_1 ^2 + 1.8X_2 ^2 {\text{ (in coded form) and}}$$ $$Y = 24.4 - .051X_1 - .157X_2 - .00025X_1 X_2 - .000085X_1 ^2 + .0009X_2 ^2 {\text{ (in natural form)}}$$ (in natural form). Negative effects of heavy liming can not be explained only by pH changes.     

Long-term sulfate dynamics at lange bramke (Harz) used for testing two acidification models

At Lange Bramke (Harz) soil solution and runoff concentrations of major elements were observed over 16 yr. During this period acid deposition was high but showed a marked decrease of H⁺ and SO ₄ ^2? both in concentrations and fluxes over the last five years. Among others, this record reveals the following patterns: seasonality in the signals for SO ₄ ^2? and NO ₃ ^? in runoff which are synchronous; an accumulation of SO ₄ ^2? in the soil, initially up to 50% of the deposition fluxes; apparently no correlation between runoff and SO ₄ ^2? concentration, and no long-term trend in runoff concentration of SO ₄ ^2? . In this paper we use these patterns in the data set from Lange Bramke to test two established acidification models. The test criterion is that the algorithms employed by the SO ₄ ^2? modules of these models must be able to reproduce these features. To that end, both models need not to be run as it can be shown that even with completely unrestricted parameter values the two algorithms are unable to match the observed SO ₄ ^2? dynamics. The MAGIC model (Cosbyet al., 1985) is unable to reproduce, given the existence of net SO ₄ ^2? accumulation, the constant SO ₄ ^2? concentration in runoff during the last 16 years. The second model, BEM (Prenzel, 1986), is succesful in reconstructing the constant SC>4~ levels in runoff. However, on a monthly time scale BEM predicts a shift between the periodic maximum concentrations of SO ₄ ^2? and NO ₃ ^? which is not observed in the data.     

Speciation of Phosphorus and Cadmium in a Contaminated Soil Amended with Bone Char: Sequential Fractionations and XANES Spectroscopy

In this work, photocatalytic degradation of two reactive dyes, Reactive Yellow 84 (RY 84) and Reactive Black 5 (RB 5), on FeTiO₃/TiO₂ heterojunction in the presence of UV–visible radiation and H₂O₂ has been reported. FeTiO₃/TiO₂ heterojunction has been prepared from ilmenite FeTiO₃ and anatase TiO₂ by employing oxalic acid as an organic linker. FeTiO₃/TiO₂ ratios have been varied from 1 to 5 wt.%, and the materials were characterized by X-ray diffraction, scanning electron microscope and diffused reflectance UV–visible spectroscopic analysis. The photocatalytic activity of FeTiO₃/TiO₂ heterojunction for the degradation of the organic dyes RY 84 and RB 5 in the presence of UV–visible light was found to be higher than that of pure TiO₂. The addition of H₂O₂ increases the rate of degradation of both dyes on FeTiO₃/TiO₂ heterojunction. It facilitates the fast degradation of dye solutions even when their concentration was above 100 mg/l, which is otherwise very slow due to the low transmittance of light by the dye solution. The extent of mineralisation of the reactive dye during photocatalytic degradation was estimated from chemical oxygen demand analysis. FeTiO₃/TiO₂ heterojunction photocatalyst was also found to have good photostability; the material retains almost 97 % of its initial activity even in the fifth cycle.     

Mid-term trends in acid precipitation,streamwater chemistry and element budgets in the strengbach catchment (Vosges Mountains,France)

In the Vosges Mountains (NE of France), integrated plot-catchment studies have been carried out since 1985 in the Strengbach basin to study the influence of acid atmospheric inputs on surface water quality and element budgets. In this paper, available mid-term time series (1985–1991) have been considered to detect obvious trends, if any, in surface water chemistry and element budgets. Air quality data showed a slight decline for SO₂, whereas NO₂ slightly increased over the period, but these trends are not very significant. This is in agreement with increased N concentration (mainly as NH ₄ ⁺ ) and with the stability of SO ₄ ^2? in open field precipitation. Because of a significant decrease in rainfall amount over the period, only inputs of NH ₄ ⁺ increased significantly whereas H⁺ and SO ₄ ²⁺ inputs declined. In spring and streamwaters, pH and dissolved Si concentration increased mainly as a result of a reduced flow. Na⁺, K⁺, Cl^? and HCO-3~^? concentrations remained stable whereas Ca²⁺, Mg²⁺ and SO ₄ ²⁺ concentrations declined significantly. Only NO ₃ ^? concentration increased significantly in springwaters. The catchment budgets revealed significant losses of base cations, Si and SO ₄ ^2? . These losses decreased over the period. Nitrogen was retained in the ecosystem. However, a longer record is needed to determine whether or not changes in surface water chemistry have resulted from short-term flow reductions or long-term changes in input-output ion budgets. This is specially true with N because the decline in SO ₄ ^2? output was accompanied by N accumulation.     

Photocatalytic Efficiency of TiO<Subscript>2</Subscript> Supported on Raw Red Clay Disks to Discolour Reactive Red 141

In this work, disks containing different amount of the TiO₂ precursor impregnated on the raw red clay were produced. The disks were obtained by pressing in metal template and subsequently calcined at 500 °C. The raw clay was used as rigid support to fix the TiO₂. The materials were characterized by X-ray diffraction, diffuse reflectance spectroscopy, N₂ adsorption-desorption (BET and BJH), scanning electron microscopy, and Fourier transform infrared (FTIR) spectroscopy. The ability of disks to produce superoxide and hydroxyl radicals after photoexcitation with UV irradiation was monitored by EPR. The catalytic efficiency was evaluated by the Reactive Red 141 dye discoloration under artificial UV light and sunlight. The reaction parameters such as concentration of RR-141 and irradiation source were evaluated. The results showed that the disks were able to decolorize 97.5% under sunlight at 60 min. The disks were also efficient in the discoloration until the tenth cycle, resulting in discoloration values near the initial cycles. Additionally, the dye fragments produced in cleavage of molecule during the reaction were evaluated by LC/MS-MS.

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Comparison of Photocatalytic and Photosensitized Oxidation of Paraben Aqueous Solutions Under Sunlight

It is well-established that aquatic wildlife is exposed to natural and synthetic endocrine disrupting compounds which are able to interfere with the hormonal system. Although advanced oxidation processes (AOPs) have shown to be effective, their application is limited by a relatively high operational cost. In order to reduce the cost of energy consumed in the AOPs, widely available solar energy instead of UV light may be applied either as photocatalytic oxidation or as photosensitized oxidation. The main goal of the present study was to investigate the sunlight photodegradation of paraben mixture. Two processes, namely the photocatalytic oxidation with modified TiO₂ nanoparticles and photosensitized oxidation with photosensitive chitosan beads, were applied. The oxidants were identified as singlet oxygen and hydroxyl radicals for photosensitized and photocatalytic oxidation, respectively. The toxicity, as well as ability to water disinfection of both processes under natural sunlight, has been investigated. Application of sunlight for the processes led to degradation of parabens. The efficiency of both processes was comparable. Despite the fact that singlet oxygen is weaker oxidant than hydroxyl radicals, the photosensitized oxidation seems to be more promising for wastewater purification, due to the possibility of chitosan bead reuse and more effective water disinfection.

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Nitrate reduction coupled with microbial oxidation of sulfide in river sediment

Purpose

Nitrate (NO ₃ ^? ) is often considered to be removed mainly through microbial respiratory denitrification coupled with carbon oxidation. Alternatively, NO ₃ ^? may be reduced by chemolithoautotrophic bacteria using sulfide as an electron donor. The aim of this study was to quantify the NO ₃ ^? reduction process with sulfide oxidation under different NO ₃ ^? input concentrations in river sediment.

Materials and methods

Under NO ₃ ^? input concentrations of 0.2 to 30?mM, flow-through reactors filled with river sediment from the Pearl River, China, were used to measure the processes of potential NO ₃ ^? reduction and sulfate (SO ₄ ^2? ) production. Molecular biology analyses were conducted to study the microbial mechanisms involved.

Results and discussion

Simultaneous NO₃ ^? removal and SO₄ ^2? production were observed with the different NO ₃ ^? concentrations in the sediment samples collected at different depths. Potentially, NO ₃ ^? removal reached 72 to 91?% and SO ₄ ^2? production rates ranged from 0.196 to 0.903?mM?h^?1. The potential NO ₃ ^? removal rates were linearly correlated to the NO ₃ ^? input concentrations. While the SO ₄ ^2? production process became stable, the NO ₃ ^? reduction process was still a first-order reaction within the range of NO ₃ ^? input concentrations. With low NO ₃ ^? input concentrations, the NO ₃ ^? removal was mainly through the pathway of dissimilatory NO ₃ ^? reduction to NH ₄ ⁺ , while with higher NO ₃ ^? concentrations the NO ₃ ^? removal was through the denitrification pathway.

Conclusions

While most of NO ₃ ^? in the sediment was reduced by denitrifying heterotrophs, sulfide-driven NO ₃ ^? reduction accounted for up to 26?% of the total NO ₃ ^? removal under lower NO ₃ ^? concentrations. The vertical distributions of NO ₃ ^? reduction and SO ₄ ^2? production processes were different because of the variable bacterial communities with depth.     

Chemical Characterization of Rain and Fog Water in the Cervenohorske Sedlo (Hruby Jesenik Mountains, Czech Republic)

Field study at the Cervenohorske sedlo (1,013 m a.s.l.) (Hruby Jesenik Mountains, the Czech Republic, Central Europe) during 1999–2002 has been conducted in order to analyse the chemistry of rain/snow water using bulk and throughfall collector and fog/cloud water using modified passive Grunow collector. Fog water input to coniferous forest (Picea abies) was quantified using canopy balance method. For all samples pH, and the concentrations of $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ , Ca²⁺, K⁺, Mg²⁺, Na⁺, Cl^?, $ {\text{NO}}^{{\text{ - }}}_{{\text{3}}} $ , and $ {\text{SO}}^{{{\text{2 - }}}}_{{\text{4}}} $ were measured. The volume-weighted mean pH value varied from 4.92 to 5.43 in open bulk precipitation, from 4.30 to 4.71 in throughfall and from 4.66 to 5.23 in fog water. The fog droplets generally contain higher ion concentrations than rainwater. The related enrichment factors lie between 1.1 and 10.7 for the relevant species. The fog samples exhibit higher concentrations of $ {\text{NO}}^{{\text{ - }}}_{{\text{3}}} $ and $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ as compared to the bulk samples during 2000–2002. $ {\text{NO}}^{{\text{ - }}}_{{\text{3}}} $ are 5.7–10.7 times more concentrated in fog water and $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ are 3.4–7.2 times more concentrated in fog water. These differences may result from the height and characteristics of formation of the droplets. Based on canopy balance method, the annual fog water inputs were estimated to be 22 and 19% of rain and snow annual amounts in 1999 and 2000, respectively. For $ {\text{NO}}^{{\text{ - }}}_{{\text{3}}} $ , $ {\text{NH}}^{{\text{ + }}}_{{\text{4}}} $ , and $ {\text{SO}}^{{{\text{2 - }}}}_{{\text{4}}} $ , the contribution of fog deposition in total (bulk + fog) deposition is estimated as 54, 47, and 42%, respectively.     

Bulk Atmospheric Deposition in the Southern Po Valley (Northern Italy)

A study on pH and chemical composition of precipitation was carried out in two Italian sites, one urban (site 1) and one rural (site 2), located approximately 30 km far from Bologna, during a 3-year period. No significative site variation was found. In both locations, bulk deposition pH ranged from slightly acid to slightly alkaline, despite the volume weighted mean concentration of acidic species, NO ₃ ^? and SO ₄ ^2? (67.4 and 118.4 μeq l^?1 in site 1 and 88.7 and 103.8 μeq l^?1 in site 2), that were similar to those of typical acidic rainfall region. This might be ascribed to the neutralization reaction of the Ca²⁺, attributed to the calcareous soil and the frequent dusty air mass intrusion from the Sahara. The pair correlation matrix and the analysis of the main components suggested also ammonium and other crustal elements as neutralization agents. The depositional rate of SO ₄ ^2? and NO ₃ ^? , chemical elements of agricultural interest, amounted to 38 and 28 and 32 and 35 kg ha^?1 for site 1 and site 2, respectively. These supplies of nutrient were not negligible and had to be considered on cultivated lands. NH ₄ ⁺ deposition rate on site 2 was 7 kg ha^?1, 23% over site 1, probably due to nitrogen fertilization in the fields around the monitoring station. In site 1, SO ₄ ^2? presented a seasonal trend, indicating that its principal source was the residential heating. Results emphasized that the entity of the bulk deposition acidification is linked not only to the ions local emission sources (fossil fuel combustions, heating, and fertilizers) but also to the surrounding territory and the prevalent wind that transports through kilometers air masses which may contain acidic and alkaline species.     

Effects of TiO<Subscript>2</Subscript> Nanoparticles on the Neotropical Cladoceran <Emphasis Type="Italic">Ceriodaphnia silvestrii</Emphasis> by Waterborne and Dietary Routes

The impact of nanoparticles (NPs) in zooplankton is poorly studied, particularly when organisms are exposed through diet. Food, constituted mainly by unicellular algae, can act as an important route of contamination for zooplankton. Since unicellular algae have a high surface area in relation to their volume, NPs can interact with their cell membranes and walls, as well as with exopolysaccharides secreted by them. In the present research, we investigated both the acute effects of waterborne titanium dioxide nanoparticles (TiO₂ NPs), and its chronic effects via dietary exposure on the Neotropical freshwater zooplankton Ceriodaphnia silvestrii Daday, 1902 (Crustacea: Cladocera). The observed acute effects served as support for chronic tests, in which we investigated the effects of TiO₂ NPs on survival and life history parameters (body length, numbers of eggs, and neonates produced) of cladoceran adult females, using the freshwater cosmopolitan chlorophycean Raphidocelis subcapitata as source of contamination of TiO₂ NPs for zooplankton. R. subcapitata cells were exposed to concentrations of 0, 0.01, 1, and 10 mg L^?1 of TiO₂ NPs for 96 h, and then provided as food for females of C. silvestrii until the third brood was released. Significant toxic effects were observed in body length and total number of neonates and eggs produced by females of C. silvestrii at concentrations of 1 and 10 mg L^?1 of TiO₂ NPs. Survival was the most sensitive parameter when exposure was given via food. From the concentration of 0.01 mg L^?1 of TiO₂ NPs, there was a decrease in the survival of C. silvestrii females. The quantification of TiO₂ NPs in algae evidenced that they have retained NPs in their cells, being, therefore, an important route of exposure and toxicity of TiO₂ NPs to the studied microcrustacean.     

Increase in the abundance of cladocera at pH 5.1 in experimentally-acidified lake 223, Experimental Lakes Area,Ontario

Lake 223 in the Experimental Lakes Area, northwestern Ontario was experimentally-acidified with H₂SO₄ from 1976 to the present. Cladocerans increased in absolute and relative abundance and in total biomass when the pH of Lake 223 was lowered from 6.7 to 5.1. Comparing the cladoceran community at pH 6.7 (1974) with that at pH 5.1 (1981 to 1983), Daphnia galeata mendotae disappeared, Diaphanosoma birgei became rare, Holopedium gibberum increased in abundance and Daphnia catawba, recorded for the first time in 1980, became abundant. Bosmina longirostris became more abundant. Except for the decline in D. birgei, the changes in cladoceran species composition with acidification are consistent with known responses of these species to low pH. The increase in importance of cladocerans in 1981 to 1983 was at the expense of copepods. It was hypothesized to be caused by the decline in predation by small fish during 1981 to 1983 as acidification reduced minnow populations and inhibited reproduction in trout and sucker. The loss of the population of the invertebrate predator, the opposum shrimp, Mysis relicta, in 1979 had little effect on cladoceran biomass.     

Degradation of Di-(2-ethylhexyl) Phthalate (DEHP) by TiO2 Photocatalysis

The photocatalytic degradation of di-(2-ethylhexyl) phthalate (DEHP) in solution using titanium dioxide (TiO₂) was analyzed in this study. It was found that DEHP was completely removed in the solution after 150 min irradiation. The effect of different factors, such as photocatalyst amount, DEHP concentration, light intensity, pH, and temperature on photocatalytic degradation was investigated. The degradation mechanism of DEHP with proton and hydroxyl radicals oxidation were also studied. It is suggested that either ethylhexyl or ester chain scissions of the aliphatic part of DEHP was the dominant degradation mechanism of the process. The photocatalytic degradation process was well described by first-order reaction. The final mineralization product was carbon dioxide and the intermediate products were identified by GC-MS. Thus, the photocatalytic degradation treatment of DEHP in wastewater is a relative simple and fast method.