Acceleration of the Fe(III)EDTA(-) reduction rate in BioDeNO(x) reactors by dosing electron mediating compounds

BioDeNO(x), a novel technique to remove NO(x) from industrial flue gases, is based on absorption of gaseous nitric oxide into an aqueous Fe(II)EDTA(2-) solution, followed by the biological reduction of Fe(II)EDTA(2-) complexed NO to N(2). Besides NO reduction, high rate biological Fe(III)EDTA(-) reduction is a crucial factor for a succesful application of the BioDeNO(x) technology, as it determines the Fe(II)EDTA(2-) concentration in the scrubber liquor and thus the efficiency of NO removal from the gas phase. This paper investigates the mechanism and kinetics of biological Fe(III)EDTA(-) reduction by unadapted anaerobic methanogenic sludge and BioDeNO(x) reactor mixed liquor. The influence of different electron donors, electron mediating compounds and CaSO(3) on the Fe(III)EDTA(-) reduction rate was determined in batch experiments (21mM Fe(III)EDTA(-), 55 degrees C, pH 7.2+/-0.2). The Fe(III)EDTA(-) reduction rate depended on the type of electron donor, the highest rate (13.9mMh(-1)) was observed with glucose, followed by ethanol, acetate and hydrogen. Fe(III)EDTA(-) reduction occurred at a relatively slow (4.1mMh(-1)) rate with methanol as the electron donor. Small amounts (0.5mM) of sulfide, cysteine or elemental sulfur accelerated the Fe(III)EDTA(-) reduction. The amount of iron reduced significantly exceeded the amount that can be formed by the chemical reaction of sulfide with Fe(III)EDTA(-), suggesting that the Fe(III)EDTA(-) reduction was accelerated via an auto-catalytic process with an unidentified electron mediating compound, presumably polysulfides, formed out of the sulfur additives. Using ethanol as electron donor, the specific Fe(III)EDTA(-) reduction rate was linearly related to the amount of sulfide supplied. CaSO(3) (0.5-100mM) inhibited Fe(III)EDTA(-) reduction, probably because SO(3)(2-) scavenged the electron mediating compound.     

Pentachlorophenol association with fulvic acids from recycled wastes

The apparent water solubility of pentachlorophenol was measured at pH=6 and at 25 degrees C in pure water, aqueous solutions of three salts (NaCl, KNO(3) and CaCl(2) at 0.010, 0.10 and 1.0M) and in aqueous solutions of three fulvic acids samples extracted from a natural soil (sFA), composted sewage sludge (csFA) and composted livestock's material (lsFA). A solubility enhancement method was developed for the measurement of partition coefficients (K(oc), L/kg organic carbon). Pentachlorophenol associates strongly with the fulvic acid samples and the calculated K(oc) were the following (averages and standard deviations): (sFA) (211+/-22) x 10(2), (csFA) (253+/-26) x 10(2), (lsFA) (235+/-10) x 10(2). For comparison purposes the K(oc) for pyrene were also calculated for the three FA samples and were the following: (sFA) (119+/-10) x 10(2), (csFA) (239+/-21) x 10(2), (lsFA) (92+/-10) x 10(2). The analysis of variance (one-way ANOVA) of the effect of the type of FA sample on the solubilization of pentachlorophenol and pyrene shows that this factor causes significant differences on the aqueous solubilization of these two organic substances.     

Partitioning of hydrogen peroxide between the gas and liquid phases in the presence of surfactant

Gas-liquid phase partitioning is a key physical property that can predict the environmental fate of a compound between two phases. Several environmental factors have been known to affect the gas-liquid phase partitioning. We investigated the influence of surfactant on the gas-liquid phase partitioning of hydrogen peroxide (H(2)O(2)). The surfactant used was ammonium perfluorooctanoate (APFO). H(2)O(2) solution containing the surfactant was equilibrated in a closed system and gas phase H(2)O(2) concentration was measured by the peroxyoxalate chemiluminescence (PO-CL) method. Gas phase H(2)O(2) concentrations remained constant below the critical micelle concentration (CMC) and increased linearly with surfactant concentration above the CMC, which indicated that surfactant micelles influenced the gas-liquid phase partitioning of H(2)O(2). This result showed that H(2)O(2)-micelle interactions are less favorable than H(2)O(2)-H(2)O interactions. Surfactant monomers did not affect the gas-liquid phase partitioning of H(2)O(2) due to the absence of micelles. Solvent (methanol) effect was also investigated and showed that gas phase H(2)O(2) concentrations increased with the addition of solvent. This indicated the unfavorable interaction of H(2)O(2) with hydrophobic medium compared to hydrophilic one. It is consistent with the result that H(2)O(2)-micelles has a weaker interaction than H(2)O(2)-water because surfactant micelles are hydrocarbon-like organic phase rather than aqueous phase.     

Synergistic toxic effect of nano-Al2O3 and As(V) on Ceriodaphnia dubia

Engineered nanomaterials (ENMs) alone could negatively impact the environment and human health. However, their role in the presence of other toxic substances is not well understood. The toxicity of nano-Al(2)O(3), inorganic As(V), and a combination of both was examined with C. dubia as the model organisms. Bare nano-Al(2)O(3) particles exhibited partial mortality at concentrations of greater than 200mg/L. When As(V) was also present, a significant amount of As(V) was accumulated on the nano-Al(2)O(3) surface, and the calculated LC(50) of As(V) in the presence of nano-Al(2)O(3) was lower than that it was without the nano-Al(2)O(3). The adsorption of As(V) on the nano-Al(2)O(3) surface and the uptake of nano-Al(2)O(3) by C. dubia were both verified. Therefore, the uptake of As(V)-loaded nano-Al(2)O(3) was a major reason for the enhanced toxic effect.     

Occurrence of alternative flame retardants in indoor dust from New Zealand: indoor sources and human exposure assessment

Due to worldwide restrictions on polybrominated diphenyl ethers (PBDEs), the demand for alternative flame retardants (AFRs), such as organophosphate flame retardants (OPFRs), novel brominated FRs (NBFRs) and hexabromocyclododecanes (HBCDs), has recently increased. Little is known about human exposure to NBFRs and OPFRs and that their levels in dust have been scarcely evaluated worldwide. To increase the knowledge regarding these chemicals, we measured concentrations of five major NBFRs, ten OPFRs and three HBCD isomers in indoor dust from New Zealand homes. Dust samples were taken from living room floors (n=34) and from mattresses of the same houses (n=16). Concentrations (ngg(-1)) of NBFRs were: 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) (<2-175), decabromodiphenyl ethane (DBDPE) (<5-1430), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) (<2-2285) and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH) (<2-640). For OPFRs, concentrations (ngg(-1)) ranged between: tri-ethyl-phosphate (TEP) (<10-235), tri-n-butyl-phosphate (TnBP) (<20-7545), tris-(2-chloroethyl)-phosphate (TCEP) (<20-7605), tris-(1-chloro-2-propyl) phosphate (TCPP) (20-7615), tri-(2-butoxyethyl)-phosphate (TBEP) (50-27325), tris-(2,3-dichloropropyl)-phosphate (TDCPP) (20-16560), tri-phenyl-phosphate (TPhP) (20-35190), and tri-cresyl-phosphate (TCP) (<50-3760). HBCD concentrations fell in the range <2-4100ngg(-1). BTBPE, DBDPE, TBPH, TBEP, and TnBP showed significant positive correlation (p<0.05) between their concentrations in mattresses and the corresponding floor dust (n=16). These data were used to derive a range of plausible exposure scenarios. Although the estimated exposure is well below the corresponding reference doses (RfDs), caution is needed given the likely future increase in use of these FRs and the currently unknown contribution to human exposure by other pathways such as inhalation and diet.     

Simultaneous conversion of CHClF(2) and CH(3)Br to CH(2)CF(2)

Gas phase reaction of CHClF(2) with CH(3)Br in an alumina tube reactor at 773-1123 K as a function of various input ratios of CH(3)Br to CHClF(2) is presented. The major products detected include C(2)F(4), CH(2)CF(2), and CH(4). Minor products include CH(3)Cl, CHF(3), C(2)H(4), C(2)H(2), CH(2)CF-CF(3), and C(2)H(3)F. The reaction produces a high yield of CH(2)CF(2) (53% based on CHClF(2) feed) at 1123 K and an input molar ratio of CH(3)Br to CHClF(2) of 1.8, suggesting that the reaction potentially can be developed as a process to convert two ozone depleting substances (CHClF(2) and CH(3)Br) to a highly valuable chemical, CH(2)CF(2). The reaction of CHClF(2) with CH(3)Cl and CH(3)I was also investigated under similar reaction conditions, to assist in understanding the reaction chemistry involved in the reaction of CHClF(2) with CH(3)Br.     

Photocatalytic oxidation of NOx using composite sheets containing TiO2 and a metal compound

The photocatalytic oxidation of nitrogen oxides (NO(x)) over titanium dioxide (TiO(2)) sheets containing metal compounds (MCs) had been studied. Calcium oxide (CaO), magnesium oxide (MgO), calcium carbonate (CaCO(3)), aluminium oxide (Al(2)O(3)) and ferric oxide (Fe(2)O(3)) were used as MCs. Al(2)O(3) and Fe(2)O(3) added to the TiO(2) sheet did not affect the photooxidation of nitrogen oxides (NO(x)). The CaO sheet treated with TiO(2) sol had the greatest efficiency as a NO(x) remover under UV irradiation. It is believed that CaO has a high adsorptivity for nitrogen dioxide (NO(2)) and nitric acid (HNO(3)). The amount of NO(x) removed by a TiO(2) sheet including MC showed a tendency to increase with increasing pH of the MC suspension, i.e. there is a good correlation between the alkalinity of the MC and the retention of NO(2) and HNO(3).     

Identification of highly brominated analogues of Q1 in marine mammals

Three novel halogenated organic compounds (HOCs) have been identified in the blubber of marine mammals from coastal New England with the molecular formulae C(9)H(3)N(2)Br(6)Cl, C(9)H(3)N(2)Br(7), and C(9)H(4)N(2)Br(5)Cl. They were identified using high and low resolution gas chromatography mass spectrometry (GCMS) and appear to be highly brominated analogues of Q1, a heptachlorinated HOC suspected to be naturally produced. These compounds were found in Atlantic white sided dolphin (Lagenorhynchus acutus), bottlenose dolphin (Tursiops truncatus), common dolphin (Delphinus delphis), Risso's dolphin (Grampus griseus), harbor porpoise (Phocoena phocoena), beluga whale (Delphinapterus leucas), fin whale (Balaenoptera physalus), grey seal (Halichoerus grypus), harp seal (Phoca groenlandica) and a potential food source (Loligo pealei) with concentrations as high as 2.7 microg/g (lipid weight). The regiospecificity of C(9)H(3)N(2)Br(6)Cl is suggestive of a biogenic origin. Debromination of C(9)H(3)N(2)Br(6)Cl may be significant in the formation of C(9)H(4)N(2)Br(5)Cl.     

Simulation modeling for nitrogen removal and experimental estimation of mass fractions of microbial groups in single-sludge system

Nitrification-denitrification in a single-sludge nitrogen removal system (SSNRS; with a sufficient carbon source for denitrification) was performed. With an increase in the mixed liquor recycle ratio (R(m)) from 1 to 2, the total nitrogen (TN) removal efficiency at a lower volumetric loading rate (VLR=0.21 NH(4)(+)-N m(-3) d(-1)) increased, but the TN removal efficiency at a higher VLR (0.35 kg NH(4)(+)-N m(-3) d(-1)) decreased. A kinetic model that accounts for the mass fractions of Nitrosomonas, Nitrobacter, nitrate reducer and nitrite reducer (f(n1), f(n2), f(dn1), and f(dn2)) in the SSNRS and an experimental approach for the estimation of the mass fractions of nitrogen-related microbial groups are also proposed. The estimated f(dn1) plus f(dn2) (0.65-0.83) was significantly larger than the f(n1) plus f(n2) (0.28-0.32); the f(n1) (0.21-0.26) was larger than the f(n2) (0.05-0.07); and the f(dn1) (0.32-0.45) varied slightly with the f(dn2) (0.33-0.38). At the lower VLR, the f(dn1) plus f(dn2) increased with increasing R(m); however at the higher VLR, the f(dn1) plus f(dn2) did not increase with increasing R(m). By using the kinetic model, the calculated residual NH(4)(+)-N and NO(2)(-)-N in the anoxic reactor and NO(2)(-)-N and NO(3)(-)-N in the aerobic reactor were in fairly good agreement with the experimental data; the calculated NO(3)(-)-N in the anoxic reactor was over-estimated and the calculated NH(4)(+)-N in the aerobic reactor was under-estimated.     

Development of the high spatial resolution EMICAT2000 emission model for air pollutants from the north-eastern Iberian Peninsula (Catalonia, Spain)

Ozone (O(3)) pollution episodes take place in Catalonia (NE of the Iberian Peninsula), mainly during summertime. The complex O(3) behaviour could be understood by using a Chemical Transport Model (CTM). Emission inventories provide the spatial and temporal emissions distribution of the O(3) precursors and other pollutants required by this approach. We developed the EMICAT2000 model with high spatial (cells of 1 km(2)) and temporal (1h) resolutions, to estimate the emissions during the year 2000 from Catalonia. Total annual emissions were 107 kt yr(-1) of NO(x), 137 kt yr(-1) of NMVOC, 267 kt yr(-1) of CO, 65 kt yr(-1) of SO(2), 24 kt yr(-1) of TSP and 32,175 kt yr(-1) of equivalent CO(2). Main NO(x) sources are on-road traffic (58%) and industries (38%). Main NMVOC sources are on-road traffic (36%), vegetation (34%) and use of solvents (13%). Speciation was established according to the Carbon Bond IV mechanism. EMICAT2000 generates directly the data files required for the third generation CTM Models-3/CMAQ.     

Reduction of ferrate(VI) and oxidation of cyanate in a Fe(VI)-TiO2-UV-NCO- system

The aqueous photocatalytic degradation of cyanate (NCO(-)), which is a long-lived neurotoxin formed during the remediation of cyanide in industrial waste streams, was studied in the ferrate(VI)-UV-TiO2-NCO(-) system. Kinetics measurements of the photocatalytic reduction of ferrate(VI) were carried out as a function of [NCO(-)], [ferrate(VI)], [O(2)], light intensity (I(o)), and amount of TiO2 in suspensions at pH 9.0. The photocatalytic reduction rate of ferrate(VI) in the studied system can be expressed as -d[Fe(VI)]/dt=kI(o)(0.5) [NCO(-)] [TiO2]. The rate of photocatalytic oxidation of cyanate with ferrate(VI) was greater than the rate in the analogous system without ferrate(VI). The possibility of involvement of reactive ferrate(V) species for this enhancement was determined by studying the reactivity of ferrate(V) with NCO(-) in a homogeneous solution using a premix pulse radiolysis technique. The rate constant for the reaction of ferrate(V) and NCO(-) in alkaline medium was estimated to be (9.60+/-0.07) x 10(2) M(-1) s(-1), which is much slower than the ferrate(VI) self-decomposition reaction (k approximately 10(7) M(-1) s(-1)). An analysis of the kinetic data in the Fe(VI)-UV-TiO2-NCO(-) system suggests that ferrate(V) is not directly participating in the oxidation of cyanate. Possible reactions in the system are presented to explain results of ferrate(VI) reduction and oxidation of cyanate.     

Effects of experimental parameters on NF(3) decomposition fraction in an oxygen-based RF plasma environment

Clean procedure is one of the major emitters of perfluorinated compounds (PFCs) in semiconductor manufacturing. Nitrogen trifluoride (NF(3)) is increasingly the process gas of choice for eliminating PFC emissions. However, its toxic to human and similar global warming potential compared to most other PFCs made NF(3) warranted much more investigation. This study demonstrated a radio-frequency plasma system for decomposing NF(3). The effects of experimental parameters: input power, O(2)/NF(3) ratio, operational pressure and NF(3) feeding concentration on NF(3) decomposition fraction (eta(NF3)) and energy efficiency E(NF3) were examined in detail. The analytical results demonstrated that the NF(3) was almost completely decomposed (>99%) at input power=30W, [NF(3)](in)=1.0% and eta(NF3) increased with input power. However, adding O(2) to the system inhibited NF(3) decomposition and decreased E(NF3). Moreover, eta(NF3) and E(NF3), decreased with gradually increasing operational pressure. Notably, increasing the NF(3) feeding concentration increased molecule density, reducing eta(NF3), but increasing E(NF3). Furthermore, the products detected in the NF(3)/O(2)/Ar plasma system were NO(2), NO, N(2)O, SiF(4), N(2) and F(2). Potential reaction pathways in the oxygen-based NF(3) plasma environment were built-up and elucidated.     

Assessment of the bioavailability of rare earth elements in soils by chemical fractionation and multiple regression analysis

The bioavailability of rare earth elements (REEs) in soils was evaluated, based on the combination of chemical fractionation and multiple regression analysis. REEs in soils were partitioned by a sequential extraction procedure into water soluble (F(ws)), exchangeable (F(ec)), bound to carbonates (F(cb)), bound to organic matter (F(om)), bound to Fe-Mn oxides (F(fm)) and residual (F(rd)) fractions. Alfalfa (Medicago Staiva Linn.) had been grown on the soils in a pot-culture experiment under greenhouse conditions for 35 days. The concentrations of REEs in fractions and plant were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Chemical fractionation showed that (F(ws)) fraction of REEs was less than 0.1% and residual (F(rd)) was the dominant form, more than 60% in soils. Bioaccumulation of REEs was observed in Alfalfa. REE availability to the plant was evaluated by multiple regression analysis. F(ws), F(ec), F(cb) and F(om) fractions were significantly correlated with REE uptake by alfalfa. But the exchangeable Pr(F(ec)) was significantly correlated with Pr concentration in alfalfa. F(ec), F(cb) and F(om) greatly contributed to La and Nd bioavailability; F(ec) and F(om) to Ce, Gd and Dy; F(ec) and F(cb) to Yb; and F(ws), F(ec) and F(om) to total REEs. This meant that the bioavailability of different species of REEs varied with individual REE. The results of this study indicated that the sequential extraction procedure, in conjunction with multiple regression analysis, may be useful for the prediction of plant uptake of REEs from soils.     

Biodegradability and toxicity assessment of trans-chlordane photochemical treatment

The removal of trans-chlordane (C(10)H(6)Cl(8)) from aqueous solutions was studied using UV, UV/H(2)O(2), UV/H(2)O(2)/Fe(2+), UV/TiO(2), or UV/TiO(2)/H(2)O(2) treatment using either UV/Vis blue lamps or UVC lamps (254 nm). H(2)O(2), FeSO(4) and TiO(2) were added at 1700, 456, and 2500 mgL(-1), respectively. trans-Chlordane was not significantly removed in non-irradiated controls and in samples irradiated with UV/Vis. It was also not removed in the absence of surfactant Triton X-114 added at 250 mgL(-1). In the presence of the surfactant, trans-chlordane concentration was reduced by 95-100% after 48 h of UVC and UVC/H(2)O(2) treatments and 70-80% after UVC/H(2)O(2)/Fe(2+), UVC/TiO(2) and UVC/H(2)O(2)/TiO(2) treatments. Based on these results, UVC, UVC/H(2)O(2) and UVC/TiO(2) treatments were further investigated. UVC treatment supported the highest pollutant removal (100% in 48 h), dechlorination efficiency (81% in 48 h), and detoxification to Lepidium sativum seed germination and activated sludge respiration although irradiated samples remained toxic to Chlorella vulgaris. Biodegradation of the UVC irradiated samples removed the source of algae toxicity but this could not be clearly attributed to the removal of trans-chlordane photoproducts because the surfactant interfered with the chemical and biological assays. Evidence was found that trans-chlordane was photodegraded through photolysis causing its successive dechlorination. trans-Chlordane removal was well described by a first order kinetic model at a rate of 0.21±0.01h(-1) at the 95% confidence interval.     

Kinetics and mechanism of nitrite oxidation by hypochlorous acid in the aqueous phase

The rate coefficient for the reaction of nitrite with hypochlorite and hypochlorous acid has been studied using spectrophotometric measurements. The reaction rate has been determined in a wide range of H(+) concentration (5< or =-log[H(+)]< or =11). The kinetics were carried out as a function of NO(2)(-), H(+) and total hypochlorite ([HOCl](total)=[HOCl]+[ClO(-)]+[ClNO(2)]) concentrations. The observed overall rate law is described by: -d[HClO](T)dt=[a[NO(2)(-)](2)+b[NO(2)(-)]][H(+)](2)c+d[H(+)]+e[NO(2)(-)][H(+)](2)[HOCl](total)At T=298 K and in Na(2)SO(4) at an ionic strength (I=1.00 M), we obtained using a nonlinear fitting procedure: a=(1.83+/-0.36)x10(7) s(-1), b=(1.14+/-0.23)x10(5) Ms(-1), c=(1.12+/-0.17)x10(-13) M, d=(1.43+/-0.29)x10(-6) M(2) and e=(1.41+/-0.28)x10(3) M where the errors represent 2sigma. According to the overall rate law, a/b=k(1)/k(3), b/e=k(3), c=K(w), d/c=K(a), d=K(a)K(w) and e=K(1)K(a). In Na(2)SO(4) at an ionic strength (I=1.00 M), the values of K(1) and K(a) are (1.1+/-0.1)x10(-4) and 1.28x10(7) M(-1), respectively. A mechanism is proposed for the NO(2)(-) oxidation which involves the reversible initial step: NO(2)(-)+HOCl left harpoon over right harpoon ClNO(2)+OH(-) (K(1)), while ClNO(2) undergoes the two parallel reactions: attack by NO(2)(-) (k(1)) and hydrolysis (k(3)). ClNO(2) and N(2)O(4) are proposed as important intermediates as they control the mechanism. The rate coefficients k(1) and k(3) have been determined at different ionic strengths in NaCl and Na(2)SO(4). The influence of the ionic strength and ionic environment has been studied in this work.     

Interactive effects of ozone and elevated carbon dioxide on the growth and physiology of black cherry, green ash, and yellow-poplar seedlings

Potted seedlings of black cherry (Prunus serotina Ehrh.) (BC), green ash (Fraxinus pennsylvanica Marsh.) (GA), and yellow-poplar (Liriodendron tulipifera L.) (YP) were exposed to one of the four treatments: (1) charcoal-filtered air (CF) at ambient CO(2) (control); (2) twice ambient O(3) (2 x O(3)); (3) twice ambient CO(2) (650 microl l(-1)) plus CF air (2 x CO(2)); or (4) twice ambient CO(2) (650 microl l(-1)) plus twice ambient O(3) (2 x CO(2) + 2 x O(3)). The treatments were duplicated in eight continuously stirred tank reactors for 10 weeks. Gas exchange was measured during the last 3 weeks of treatment and all seedlings were destructively harvested after 10 weeks. Significant interactive effects of O(3) and CO(2) on the gas exchange of all three species were limited. The effects of elevated CO(2) and O(3), singly and combined, on light-saturated net photosynthesis (A(max)) and stomatal conductance (g(s)) were inconsistent across species. In all three species, elevated O(3) had no effect on g(s). Elevated CO(2) significantly increased A(max) in GA and YP foliage, and decreased g(s) in YP foliage. Maximum carbon exchange rates and quantum efficiencies derived from light-response curves increased, while compensation irradiance and dark respiration decreased in all three species when exposed to 2 x CO(2). Elevated O(3) affected few of these parameters but any change that was observed was opposite to that from exposure to 2 x CO(2)-air. Interactive effects of CO(2) and O(3) on light-response parameters were limited. Carboxylation efficiencies, derived from CO(2)-response curves (A/C(i) curves) decreased only in YP foliage exposed to 2 x CO(2)-air. In general, growth was significantly stimulated by 2 x CO(2) in all three species; though there were few significant growth responses following exposure to 2 x O(3) or the combination of 2 x CO(2) plus 2 x O(3). Results indicate that responses to interacting stressors such as O(3) and CO(2) are species specific.     

Different reaction mechanisms of diphenylether and 4-bromodiphenylether with nitrous acid in the 355 nm laser flash photolysis of mixed aqueous solution

The microscopic reaction mechanisms of diphenylether (DPE) and 4-bromodiphenylether (4-BrDPE) with nitrous acid (HNO(2)) in the absence of O(2) have been explored by the 355nm laser flash photolysis. It was proposed that OH radical, from the photolysis of HNO(2), added to DPE forms the C(12)H(10)O-OH adduct while added to 4-BrDPE forms the 4-BrDPE-OH and 4-BrOH-DPE adducts. The first-order decay rate constants of the C(12)H(10)O-OH adduct, 4-BrDPE-OH adduct and 4-BrOH-DPE adduct were measured to be (1.86+/-0.14)x10(5)s(-1), (2.19+/-0.04)x10(5)s(-1) and (1.56+/-0.03)x10(5)s(-1), respectively. The final photolysis products of DPE and HNO(2) identified by GC/MS analysis were phenol, o-hydroxydiphenylether, p-hydroxydiphenylether and p-nitrodiphenylether, while the final photolysis product of 4-BrDPE and HNO(2) identified by LC/MS analysis was mainly the dimer.     

Influence of the colloid type on the transfer of 60Co and 85Sr in silica sand column under varying physicochemical conditions

The influence of two types of colloids (natural organic matter, NOM), a colloid with high affinity for radionuclides (RN(s)), and hydrophilic synthetic latex (SHL), a colloid with low affinity for RN(s) on the transfer of (60)Co and (85)Sr in a silica sand column was studied under different physicochemical conditions: pH (4.9), ionic strength (10(-3) M and 10(-2) M), concentration of colloids (100 mg l(-1), 10 mg l(-1)), flow velocity (12.4 cm h(-1) and 3.7 cm h(-1)), water saturation of the column (100% and 70%). In the absence of colloids, the transfer of (60)Co and (85)Sr was retarded compared to the transfer of the conservative tracer. In the presence of colloids and according to the specific physicochemical conditions, an acceleration or retardation of (60)Co and (85)Sr transfer was observed compared to their transfer in the absence of colloids. Our results evidenced that any colloids even with low reactivity could significantly modify the RN transfer. However, the extent to which the transfer was influenced differs according to the colloid type; the NOM exhibiting higher impact than SHL. Batch experiments helped in interpreting of the interactions between the colloids, RN(s) and solid phase observed in column.     

Oxidative transformations of environmental pharmaceuticals by Cl₂, ClO₂, O₃, and Fe(VI): kinetics assessment

Several pharmaceuticals have been detected globally in surface water and drinking water, which indicate their insufficient removal from water and wastewater using conventional treatment methods. This paper reviews the kinetics of oxidative transformations of pharmaceuticals (antibiotics, lipid regulators, antipyretics, anticonvulsants, and beta-blockers) by Cl(2), ClO(2), O(3), and ferrate(VI) (Fe(VI)O(4)(2-),Fe(VI)) under treatment conditions. In the chlorination of sulfonamide antibiotics, HOCl is the major reactive Cl(2) species whereas in the oxidation by Fe(VI), HFeO(4)(-) is the dominant reactive species. Both oxidation processes can oxidize sulfonamides in seconds at a neutral pH (t(1/2)≤ 220 s; 1 mg L(-1) HOCl or K(2)FeO(4)). The reactivity of O(3) with pharmaceuticals is generally higher than that of HOCl (k(app,pH 7) (O(3))=1-10(7)M(-1)s(-1); k(app,pH 7) (HOCl)=10(-2)-10(5)M(-1)s(-1)). Ozone selectively oxidizes pharmaceuticals and reacts mainly with activated aromatic systems and non-protonated amines. Oxidative transformation of most pharmaceuticals by O(3) occurs in seconds (t(1/2)≤ 100 s; 1 mg L(-1) O(3)) while half-lives for oxidations by HOCl differ by at least two orders of magnitude. Ozone appears to be efficient in oxidizing pharmaceuticals in aquatic environments. The limited work on Fe(VI) shows that it can also potentially transform pharmaceuticals in treatment processes.