Photocatalytic degradation of dichlorvos in aqueous TiO<Subscript>2</Subscript> suspensions

Introduction  

In the present work, we explored the kinetics of dichlorvos (2,2-dichlorvinyl dimethyl phosphate, DDVP) decay through UV-A light-induced TiO₂ photocatalysis at pH 4 and 9, and the formation of degradation intermediates and final products under specific experimental conditions. Experimental observations and theoretical considerations allowed us to suggest the degradation mechanism of DDVP by the UV/TiO₂ process in aqueous solution.     

Degradation of 2,4-D in soils by Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles combined with stimulating indigenous microbes

Purpose  

Degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) in soils by Fe₃O₄ nanoparticles combined with soil indigenous microbes was investigated, and the effects of Fe₃O₄ nanoparticles on soil microbial populations and enzyme activities were also studied.     

Effect of Pb toxicity on leaf growth, antioxidant enzyme activities, and photosynthesis in cuttings and seedlings of Jatropha curcas L

Background  

Cuttings and seedlings of Jatropha curcas L. were exposed to different regimes of lead (Pb) stress as Pb(NO₃)₂ at 0 (CK), 0.5, 1, 2, 3, and 4 mM kg⁻¹ soil.     

Ferrate(VI) enhanced photocatalytic oxidation of pollutants in aqueous TiO<Subscript>2</Subscript> suspensions

Background, aim and scope  

Photocatalytic oxidation using UV irradiation of TiO₂ has been studied extensively and has many potential industrial applications, including the degradation of recalcitrant contaminants in water and wastewater treatment. A limiting factor in the oxidation process is the recombination of conduction band electrons (e ⁻ _cb) with electron holes (h_vb⁺) on the irradiated TiO₂ surface; thus, in aqueous conditions, the presence of an effective electron scavenger will be beneficial to the efficiency of the oxidation process. Ferrate (FeO₄²⁻) has received much recent attention as a water treatment chemical since it behaves simultaneously as an oxidant and coagulant. The combination of ferrate [Fe(VI)] with UV/TiO₂ photocatalysis offers an oxidation synergism arising from the Fe(VI) scavenging of e ⁻ _cb and the corresponding beneficial formation of Fe(V) from the Fe(VI) reduction. This paper reviews recent studies concerning the photocatalytic oxidation of problematic pollutants with and without ferrate.     

Simultaneous extraction of Cr(VI) and Cu(II) from humic acid with new synthesized EDTA derivatives

Soil washing is one of the few permanent treatment alternatives for removing metal contaminants. Ethylenediaminetetraacetic acid and its salts (EDTA) is very effective at removing cationic metals and has been utilized globally. However it is ineffective for anionic metal contaminants or metals bound to soil organic matter. The simultaneous removal of cationic and anionic metal contaminants by soil washing is difficult due to differences in their properties. The present study evaluated the potential of a washing process using two synthesized EDTA-derivatives, C₆HEDTA (2,2′-((2-((carboxymethyl)(2-(hexanoyloxy)ethyl)amino)ethyl)azanediyl)diacetic acid) and C₁₂HEDTA (2,2′-((2-((carboxymethyl) (2-(dodecanoyloxy)ethyl)amino)ethyl)azanediyl)diacetic acid), which consist of a hydrophilic polycarboxylic moiety and a hydrophobic moiety with a monoalkyl ester group. A series of equilibrium batch experiments at room temperature were conducted to investigate the efficacy of C₆HEDTA and C₁₂HEDTA as extractants for both oxyanion Cr(VI) and cationic Cu(II). Results showed that either C₆HEDTA or C₁₂HEDTA can extract both Cr(VI) and Cu(II) from humic acid simultaneously. However, C₆HEDTA was less effective for Cr(VI) probably because it has no surface activities to increase solubility of humic acid, like C₁₂HEDTA. Extraction of Cr(VI) was mainly attributed to the decreased surface tension and enhanced solubility of organic matter. Extraction of Cu(II) was attributed to both the Cu(II) chelation and enhanced solubility of humic acid. It was demonstrated that the hydrophilic polycarboxylic moiety of C₁₂HEDTA chelates cations while the monoalkyl ester group produces surface active properties that enhance the solubility of humic acid.     

Acute toxicity assessment of explosive-contaminated soil extracting solution by luminescent bacteria assays

Explosive-contaminated soil is harmful to people’s health and the local ecosystem. The acute toxicity of its extracting solution was tested by bacterial luminescence assay using three kinds of luminescent bacteria to characterize the toxicity of the soil. An orthogonal test L ₁₆ (4⁵) was designed to optimize the soil extracting conditions. The optimum extracting conditions were obtained when the ultrasonic extraction time, ultrasonic extraction temperature, and the extraction repeat times were 6 h, 40 °C, and three, respectively. Fourier transform infrared spectroscopy (FTIR) results showed that the main components of the contaminated soil’s extracting solution were 2,4-dinitrotoluene-3-sulfonate (2,4-DNT-3-SO₃ ⁻); 2,4-dinitrotoluene-5-sulfonate (2,4-DNT-5-SO₃ ⁻); and 2,6-dinitrotoluene (2,6-DNT). Compared with Photobacterium phosphoreum and Vibrio fischeri, Vibrio qinghaiensis sp. Nov. is more suitable for assessing the soil extracting solution’s acute toxicity. Soil washing can remove most of the contaminants toxic to luminescent bacterium Vibrio qinghaiensis sp. Nov., suggesting that it may be a potential effective remediation method for explosive-contaminated soil.

     

Trace gas variations at Cape Point,South Africa,during May 1997 following a regional biomass burning episode

During the continuous monitoring of atmospheric parameters at the station Cape Point (34°S, 18°E), a smoke plume originating from a controlled fire of 30-yr-old fynbos was observed on 6 May 1997. For this episode, which was associated with a nocturnal inversion and offshore airflow, atmospheric parameters (solar radiation and meteorological data) were considered and the levels of various trace gases compared with those measured at Cape Point in maritime air. Concentration maxima in the morning of 6 May for CO₂, CO, CH₄ and O₃ amounted to 370.3 ppm, 491 ppb, 1730 ppb and 47 ppb, respectively, whilst the mixing ratios of several halocarbons (F-11, F-12, F-113, CCl₄ and CH₃CCl₃) remained at background levels. In the case of CO, the maritime background level for this period was exceeded by a factor of 9.8. Differences in ozone levels of up to 5 ppb between air intakes at 4 and 30 m above the station (located at 230 m above sea level) indicated stratification of the air advected to Cape Point during the plume event. Aerosols within the smoke plume caused the signal of global solar radiation and UV–A to be attenuated from 52.4 to 13.0 mW cm⁻² and from 2.3 to 1.3 mW cm⁻², respectively, 5 h after the trace gases had reached their maxima. Emission ratios (ERs) calculated for CO and CH₄ relative to CO₂ mixing ratios amounted to 0.042 and 0.0040, respectively, representing one of the first results for fires involving fynbos. The CO ER is somewhat lower than those given in the literature for African savanna fires (average ER=0.048), whilst for CH₄ the ER falls within the range of ERs reported for the flaming (0.0030) and smouldering phases (0.0055) of savanna fires. Non-methane hydrocarbon (NMHC) data obtained from a grab sample collected during the plume event were compared to background levels. The highest ERs (ΔNMHC/ΔCH₄) have been obtained for the C₂–C₃ hydrocarbons (e.g. ethene at 229.3 ppt ppb⁻¹), whilst the C₄–C₇ hydrocarbons were characterised by the lowest ERs (e.g. n-hexane at 1.0 and n-pentane at 0.8 ppt ppb⁻¹).     

Photochemical transformation of the thyroid hormone levothyroxine in aqueous solution

Purpose  

The direct aqueous photolysis of the thyroid hormone levothyroxine (T₄) has been studied.     

Response of denitrification genes <Emphasis Type="Italic">nirS</Emphasis>, <Emphasis Type="Italic">nirK</Emphasis>, and <Emphasis Type="Italic">nosZ</Emphasis> to irrigation water quality in a Chinese agricultural soil

Purpose  

Denitrification is an important biochemical process in global nitrogen cycle, with a potent greenhouse gas product N₂O. Wastewater irrigation can result in the changes of soil properties and microbial communities of agricultural soils. The purpose of this study was to examine how the soil denitrification genes responded to different irrigation regimes.     

Nitric oxide and nitrous oxide emission from Hungarian forest soils; linked with atmospheric N-deposition

Studies of forest nitrogen (N) budgets generally measure inputs from the atmosphere in wet and dry deposition and outputs via hydrologic export. Although denitrification has been shown to be important in many wetland ecosystems, emission of N oxides from forest soils is an important, and often overlooked, component of an ecosystem N budget. During 1 year (2002–03), emissions of nitric oxide (NO) and nitrous oxide (N₂O) were measured from Sessile oak and Norway spruce forest soils in northeast Hungary. Accumulation in small static chambers followed by gas chromatography-mass spectrometry detection was used for the estimation of N₂O emission flux. Because there are rapid chemical reactions of NO and ozone, small dynamic chambers were used for in situ NO flux measurements. Average soil emissions of NO were 1.2 and 2.1 μg N m⁻² h⁻¹, and for N₂O were 15 and 20 μg N m⁻² h⁻¹, for spruce and oak soils, respectively. Due to the relatively high soil water content, and low C/N ratio in soil, denitrification processes dominate, resulting in an order of magnitude greater N₂O emission rate compared to NO. The previously determined N balance between the atmosphere and the forest ecosystem was re-calculated using these soil emission figures. The total (dry+wet) atmospheric N-deposition to the soil was 1.42 and 1.59 g N m⁻² yr⁻¹ for spruce and oak, respectively, while the soil emissions are 0.14 and 0.20 g N m⁻² yr⁻¹. Thus, about 10–13% of N compounds deposited to the soil, mostly as and , were transformed in the soil and emitted back to the atmosphere, mostly as greenhouse gas (N₂O).     

Photochemical production and loss of organic acids in high Arctic aerosols during long-range transport and polar sunrise ozone depletion events

Unique daily measurements of water-soluble organics in fine (<2 μm) and coarse (>2 μm) aerosols were conducted at Alert in the Canadian Arctic in winter to spring of 1992. They yield insight into photochemical production and loss of organics during long-range transport and ozone depletion events following polar sunrise. Comprehensive analyses of α, ω-dicarboxylic acids (C₂–C₁₂), ω-oxocarboxylic acids (C₂–C₉) and α-dicarbonyls (C₂, C₃) as well as pyruvic acid and aromatic (phthalic) diacid were conducted using GC and GC/MS techniques. Oxalic (C₂) acid was generally the dominant diacid species in both fine and coarse fractions, followed by malonic (C₃) and succinic (C₄) acids. Concentrations of total diacids in the fine aerosol fraction (0.2–64 ng m⁻³) were 5–60 times higher than those in the coarse fraction (0.01–3 ng m⁻³). After polar sunrise in early-March, the total concentration of fine aerosol diacids increased by a factor of 3–5 while the coarse mode did not change significantly. From dark winter to sunlit spring, temporal changes in correlations and ratios of these water-soluble organics to vanadium and sulfate measured simultaneously suggest that atmospheric diacids and related organic compounds are largely controlled by long-range atmospheric transport of polluted air during winter, but they are significantly affected by photochemical production. The latter can occur in sunlight either during transport to the Arctic or during photochemical events associated with surface ozone depletion and bromine chemistry near Alert in spring. Conversion of gaseous precursors to particulate matter via photochemical oxidation was intensified at polar sunrise, resulting in a peak in the ratio of total diacids to V. During ozone depletion events, complex patterns are indicated in photochemical production and loss depending on the diacid compound. Unsaturated (maleic and phthalic) diacids were inversely correlated with particulate Br whereas saturated diacids (C₂–C₄) positively correlated with particulate Br. These results suggest that Br chemistry associated with ozone depletion leads to degradation of unsaturated diacids and to the production of smaller saturated diacids.     

Winter-grazing reduces methane uptake by soils of a typical semi-arid steppe in Inner Mongolia,China

Steppe ecosystems are regarded as an important sink of atmospheric methane (CH₄) and grazing is hypothesized to reduce CH₄ uptake. However, firm experimental evidence is required to prove this hypothesis. Using a fully automated, chamber-based measuring system, we conducted continuous high-frequency (at a 3-h interval) measurements of CH₄ uptake in a Leymus chinensis steppe, which is a typical grassland ecosystem in Inner Mongolia, China. Two management regimes were investigated: ungrazed since 1999 (UG99) and winter-grazed since 2001 (WG01). Measurements were carried out continuously during the periods of June–September 2004, May–September 2005 and March–June 2006. During all of these periods, significantly lower mean CH₄ uptake (±S.E.) at WG01 (28±0.7 μg C m⁻² h⁻¹) as compared to UG99 (56±1.0 μg C m⁻² h⁻¹) (p<0.01) was found. Total CH₄ uptake during the growing seasons (May–September) 2004 and 2005 at WG01 and UG99 was quantified as 1.15 and 2.15 kg C ha⁻¹, respectively. Annual rates of CH₄ uptake were approximately 1.91 (WG01) and 3.58 kg C ha⁻¹ (UG99), respectively. These results indicate that winter-grazing of steppe significantly reduced atmospheric CH₄ uptake by ca. 47%. The winter-grazing practice may have inhibited CH₄ uptake by (a) increasing the likelihood of physiological water stress for CH₄-consuming bacteria during dry periods, (b) decreasing gas diffusion into the soil and, (c) reducing the populations of CH₄ oxidizing bacteria. These three mechanisms could have collectively or independently facilitated the observed inhibitory effects. Our results suggest that grazing exerts a considerable negative impact on CH₄ uptake in semi-arid steppes at regional scales. Notwithstanding, further studies involving year-round, intensive measurements of CH₄ uptake are needed.     

Effect of organic amendments on the mobility of trace elements in phytoremediated techno-soils: role of the humic substances

The efficiency of aided phytostabilization using organic amendments such as ramial chipped wood (RCW) and composted sewage sludge (CSS) was studied on contaminated techno-soils, on nine experimental plots. The objective was to characterize the role of fulvic (FA) and humic acids (HA) on the mobilization of trace elements, specifically As, Cu, Mo, Pb and Zn. Results showed that the addition of CSS increased the total organic carbon and nitrogen content more than with RCW and as a result, the C/N ratio in the CSS soil was higher than in the RCW and non-amended (NE) soil, reflecting the high decomposition of soil organic matter in the CSS soil compared with the other soils. The RCW and CSS amendments increased the hydrogen index (HI) values and the oxygen index (OI) values compared with the NE soil, especially for the soil treated with CSS which contained more aliphatic than aromatic compounds. The addition of CSS to the techno-soil significantly increased the percentage of C _org associated with the HA fractions compared with the RCW and NE soils. The soil amended with CSS showed the highest E ₄/E ₆ ratio and the lowest E ₂/E ₃ ratio of FA. Zn and As were more abundant in the FA fraction than in the HA fraction, whereas Pb, Cu and Mo were more associated to HA than to FA in the treated and untreated soils, which may explain the difference in their mobility and availability.     

Increases of dissolved organic carbon in temperate and boreal lakes in Quebec, Canada

Purpose  

Increases in dissolved organic carbon (DOC) concentrations have been reported in surface waters worldwide in the last 10 to 20 years. The causes behind these increases have been attributed to many factors, including climate change and decreasing depositions of atmospheric sulphate ( \textSO₄^{2 -} {\text{SO}}_4^{{{2} - }} ). Trends in DOC concentrations and their potential causal factors were examined in a network of 30 lakes lying in undisturbed temperate and boreal catchments in the province of Quebec, Canada.     

Laboratory studies on the uptake of aromatic hydrocarbons by ice crystals during vapor depositional crystal growth

Uptake of aromatic hydrocarbons (AH) by ice crystals during vapor deposit growth was investigated in a walk-in cold chamber at temperatures of 242, 251, and 260 K, respectively. Ice crystals were grown from ambient air in the presence of gaseous AH namely: benzene (C₆H₆), toluene (methylbenzene, C₇H₈), the C₈H₁₀ isomers ethylbenzene, o-, m-, p-xylene (dimethylbenzenes), the C₉H₁₂ isomers n-propylbenzene, 4-ethyltoluene, 1,3,5-trimethylbenzene (1,3,5-TMB), 1,2,4-trimethylbenzene (1,2,4-TMB), 1,2,3-trimethylbenzene (1,2,3-TMB), and the C₁₀H₁₄ compound tert.-butylbenzene. Gas-phase concentrations calculated at 295 K were 10.3–20.8 μg m⁻³. Uptake of AH was detected by analyzing vapor deposited ice with a very sensitive method composed of solid-phase micro-extraction (SPME), followed by gas chromatography/mass spectrometry (GC/MS).Ice crystal size was lower than 1 cm. At water vapor extents of 5.8, 6.0 and 8.1 g m⁻³, ice crystal shape changed with decreasing temperatures from a column at a temperature of 260 K, to a plate at 251 K, and to a dendrite at 242 K. Experimentally observed ice growth rates were between 3.3 and 13.3×10⁻³ g s⁻¹ m⁻² and decreased at lower temperatures and lower value of water vapor concentration. Predicted growth rates were mostly slightly higher.Benzene, toluene, ethylbenzene, and xylenes (BTEX) were not detected in ice above their detection limits (DLs) of 25 pg g_ice⁻¹ (toluene, ethylbenzene, xylenes) and 125 pg g_ice⁻¹ (benzene) over the entire temperature range. Median concentrations of n-propylbenzene, 4-ethyltoluene, 1,3,5-TMB, tert.-butylbenzene, 1,2,4-TMB, and 1,2,3-TMB were between 4 and 176 pg g_ice⁻¹ at gas concentrations of 10.3–10.7 μg m⁻³ calculated at 295 K. Uptake coefficients (K) defined as the product of concentration of AH in ice and density of ice related to the product of their concentration in the gas phase and ice mass varied between 0.40 and 10.23. K increased with decreasing temperatures. Values of Gibbs energy (ΔG) were between −4.5 and 2.4 kJ mol⁻¹ and decreased as temperatures were lowered. From the uptake experiments, the uptake enthalpy (ΔH) could be determined between −70.6 and −33.9 kJ mol⁻¹. The uptake entropy (ΔS) was between −281.3 and −126.8 J mol⁻¹ K⁻¹. Values of ΔH and ΔS were rather similar for 4-ethlytoluene, 1,3,5-TMB and tert.-butylbenzene, whereas 1,2,3-TMB showed much higher values.     

Effects of soil type on leaching and runoff transport of rare earth elements and phosphorous in laboratory experiments

Introduction  

Through leaching experiments and simulated rainfall experiments, characteristics of vertical leaching of exogenous rare earth elements (REEs) and phosphorus (P) and their losses with surface runoff during simulated rainfall in different types of soils (terra nera soil, cinnamon soil, red soil, loess soil, and purple soil) were investigated.     

Adsorptive removal of naphthalene induced by structurally different Gemini surfactants in a soil-water system

A new generation of surfactant, Gemini surfactants, have been synthesized and have attracted the attention of various industrial and academic research groups. This study focused on the use of symmetric and dissymmetric quaternary ammonium Gemini surfactants to immobilize naphthalene onto soil particles, and is used as an example of an innovative application to remove HOC in situ using the surfactant-enhanced sorption zone. The sorption capacity of modified soils by Gemini surfactant and natural soils was compared and the naphthalene sorption efficiency, in the absence and presence of Gemini surfactants with different alkyl chain lengths, was investigated in the soil-water system. The results have shown that the increased added Gemini surfactant formed admicelles at the interface of soil/water having superior capability to retard contaminant. Symmetric and dissymmetric Gemini surfactants have opposite effect on the aspect of removing of PAH attributing to their solubilization and sorption behavior in soil-water system. Compared with the natural soil, sorption of naphthalene by Gemini-modified soil is noticeably enhanced following the order of C_12-2-16 < C_12-2-12 < C_12-2-8. However, the symmetric Gemini surfactant C_12-2-12 is the optimized one for in situ barrier remediation, which is not only has relative high retention ability but also low dosage.     

Decontamination of electronic waste-polluted soil by ultrasound-assisted soil washing

Laboratorial scale experiments were performed to evaluate the efficacy of a washing process using the combination of methyl-β-cyclodextrin (MCD) and tea saponin (TS) for simultaneous desorption of hydrophobic organic contaminants (HOCs) and heavy metals from an electronic waste (e-waste) site. Ultrasonically aided mixing of the field contaminated soil with a combination of MCD and TS solutions simultaneously mobilizes most of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and the analyte metal (Pb, Cu, and Ni) burdens. It is found that 15 g/L MCD and 10 g/L TS is an efficient reagent combination reconciling extraction performance and reagent costs. Under these conditions, the removal efficiencies of HOCs and heavy metals are 93.5 and 91.2 %, respectively, after 2 cycles of 60-min ultrasound-assisted washing cycles. By contrast, 86.3 % of HOCs and 88.4 % of metals are removed from the soil in the absence of ultrasound after 3 cycles of 120-min washing. The ultrasound-assisted soil washing could generate high removal efficiency and decrease the operating time significantly. Finally, the feasibility of regenerating and reusing the spent washing solution in extracting pollutants from the soil is also demonstrated. By application of this integrated technology, it is possible to recycle the washing solution for a purpose to reduce the consumption of surfactant solutions. Collectively, it has provided an effective and economic treatment of e-waste-polluted soil.

     

Coupling of solar-assisted advanced oxidative and biological treatment for degradation of agro-residue-based soda bleaching effluent

This study evaluates the effect of integrated solar-assisted advanced oxidation process (AOP) and biological treatment on the extent of degradation of effluents from chlorination (C) and first alkaline extraction (E₁) stages of soda pulp bleaching in agro-residue-based pulp and paper mill. Biodegradation of the effluents was attempted in suspended mode using activated sludge from the functional pulp and paper industry effluent treatment plant acclimatized to effluents in question. The photocatalytic treatment was employed using zinc oxide (ZnO) in slurry mode for decontamination of effluents in a batch manner and the degradation was evaluated in terms of reduction in chemical oxygen demand. The biological treatment (24?h) of C and E₁ effluent resulted in 30 and 57?% of degradation, respectively. Solar-induced AOP of C and E₁ effluents resulted in 53 and 43?% degradation under optimized conditions (2.5?g?L^?1 ZnO at pH?8.0) after 6?h of exposure. For C effluent, a short duration of solar/ZnO (1?h) prior to biological treatment reduced the time required at biological step from 24 to 12?h for almost same extent (92?%) of degradation. However, sequential biological treatment (24?h) followed by solar/ZnO (2?h) resulted in 85.5?% degradation. In contrast, in the case of E₁ effluent, sequential biological (24?h)?Csolar/ZnO (2?h) system effectively degrades effluent to 95.4?% as compared to 84.8?% degradation achieved in solar/ZnO (2?h)?Cbiological treatment (24?h) system. In the present study, the sequencing of photocatalysis with the biological treatment is observably efficient and technically viable process for the complete mineralization of the effluents.     

Extractability of water-soluble soil organic matter as monitored by spectroscopic and chromatographic analyses

Purpose

Cold and hot water processes have been intensively used to recover soil organic matter, but the effect of extraction conditions on the composition of the extracts were not well investigated. Our objective was to optimize the extraction conditions (time and temperature) to increase the extracted carbon efficiency while minimizing the possible alteration of water extractable organic matter of soil (WEOM).

Method

WEOM were extracted at 20°C, 60°C, or 80°C for 24?h, 10?C60?min, and 20?min, respectively. The different processes were compared in terms of pH of suspensions, yield of organic carbon, spectroscopic properties (ultraviolet?Cvisible absorption and fluorescence), and by chromatographic analyses.

Results

For extraction at 60°C, the time 30?min was optimal in terms of yield of organic carbon extracted and concentration of absorbing and fluorescent species. The comparison of WEOM 20°C, 24?h; 60°C, 30?min; and 80°C, 20?min highlighted significant differences. The content of total organic carbon, the value of specific ultraviolet absorbance (SUVA₂₅₄), the absorbance ratio at 254 and 365?nm (E ₂/E ₃), and the humification index varied in the order: WEOM (20°C, 24?h)?Conclusions For the soil chosen, extraction at 60°C for 30?min is the best procedure for enrichment in organic chemicals and minimal alteration of the organic matter.