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.     

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.     

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.     

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.     

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.     

Removing and recovering gas-phase elemental mercury by Cu(x)Co(3-x)O(4) (0.75< or = x < or =2.25) in the presence of sulphur compounds

The Hg(0) oxidation ability and reusability of Cu(x)Co(3-x)O(4) were investigated in an attempt to improve SO(2) anti-poisoning ability of metal oxide and produce more economic and effective sorbents for the control of Hg(0) emission from combustion processes. The influence of copper content on Cu(x)Co(3-x)O(4)'s (0.75< or = x < or =2.25) oxidation ability of Hg(0) in the presence of SO(2) was investigated. According to the X-ray diffraction, Brunauer-Emmett-Teller (BET) and mass balance analysis on mercury, we found that Cu(1.5)Co(1.5)O(4) showed the highest S(BET) and best Hg(0) oxidation ability. With continuous increase of x from 0.75 to 2.25, Cu(x)Co(3-x)O(4)'s SO(2) anti-poisoning ability increased. The analysis results of the X-ray photoelectron spectroscopy manifested that the adsorptive mercury species on spent Cu(1.5)Co(1.5)O(4) was HgO. The spent Cu(1.5)Co(1.5)O(4) could be regenerated by thermal decomposition at 673K and regenerated Cu(1.5)Co(1.5)O(4) showed higher Hg(0) oxidation ability due to Hg-doping. Regenerated enrichment Hg(0) was collected using activated carbon at an ambient temperature to eliminate the secondary pollution.     

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.     

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.     

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.     

Investigation of a new approach to decompose two potent greenhouse gases: photoreduction of SF(6) and SF(5)CF(3) in the presence of acetone

In this paper, we addressed the utilization of photochemical method as an innovative technology for the destruction and removal of two potent greenhouse gases, SF(6) and SF(5)CF(3). The destruction and removal efficiency (DRE) of the process was determined as a function of excitation wavelength, irradiation time, initial ratio of acetone to SF(5)X (X represented F or CF(3)), initial SF(5)X concentration, additive oxygen and water vapor concentration. A complete removal was achieved by a radiation period of 55min and 120min for SF(6)-CH(3)COCH(3) system and SF(5)CF(3)-CH(3)COCH(3) system respectively under 184.9nm irradiation. Extra addition of water vapor can enhance DRE by approximately 6% points in both systems. Further studies with GC/MS and FT-IR proved that no hazardous products such as S(2)F(10), SO(2)F(2), SOF(2), SOF(4) were generated in this process.     

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.     

Kinetics of OH radical reactions with dibenzo-p-dioxin and selected chlorinated dibenzo-p-dioxins

The pulsed laser photolysis/pulsed laser-induced fluorescence (PLP/PLIF) technique has been applied to obtain rate coefficients for OH + dioxin (DD) (k1), OH + 2-chlorodibenzo-p-dioxin (2-CDD) (k2), OH + 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD) (k3), OH + 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) (k4), OH + 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) (k5), OH + 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) (k6), and OH + octachlorodibenzo-p-dioxin (OCDD) (k7) over an extended range of temperature. The atmospheric pressure (740 +/- 10 Torr) rate measurements are characterized by the following Arrhenius parameters (in units of cm3 molecule(-1) s(-1), error limits are 1 omega): k1(326-907 K) = (1.70+/-0.22) x 10(-12)exp(979+/-55)/T, k2(346-905 K) = (2.79+/-0.27) x 10(-12)exp(784+/-54)/T, k3(400-927 K) = 10(-12)exp(742+/-67)/T, k4(390-769 K) = (1.10+/-0.10) x 10(-12)exp(569+/-53)/T, k5(379-931 K) = (1.02+/-0.10) x 10(-12)exp(580+/-68)/T, k6(409-936 K) = (1.66+/-0.38) x 10(-12)exp(713+/-114)/T, k7(514-928 K) = (3.18+/-0.54) x 10(-12)exp(-667+/-115)/T. The overall uncertainty in the measurements, taking into account systematic errors dominated by uncertainty in the substrate reactor concentration, range from a factor of 2 for DD, 2-CDD, 2,3-DCDD, 2,7-DCDD, and 2,8-DCDD to +/- a factor of 4 for 1,2,3,4-TCDD and OCDD. Negative activation energies characteristic of an OH addition mechanism were observed for k1-k6. k7 exhibited a positive activation energy. Cl substitution was found to reduce OH reactivity, as observed in prior studies at lower temperatures. At elevated temperatures (500 K < T < 500 K), there was no experimental evidence for a change in reaction mechanism from OH addition to H abstraction. Theoretical calculations suggest that H abstraction will dominate OH reactivity for most if not all dioxins (excluding OCDD) at combustion temperatures (>1000 K). For OCDD, the dominant reaction mechanism at all temperatures is OH addition followed by Cl elimination.     

A two-generational reproductive toxicity study of zinc in rats

A two-generation reproductive toxicity study of zinc chloride (ZnCl(2)) was conducted in rats. F(o) male and female rats were administered 0.00 (control), 7.50 (low), 15.00 (mid) and 30.00 (high) mg/kg/day of ZnCl(2). Selected F(1) male and female rats were exposed to the same doses received by their parents (F(o)). Exposure of F(0) parental rats to ZnCl(2) showed significant reduction in fertility, viability (days 0 and 4), and the body weight of F(1) pups from the high-dose group but caused no effects on litter size, weaning index, and sex ratio. Similarly, the continued exposure of F(1) parental rats to ZnCl(2) also reduced fertility, liter size, viability (day 0), and the body weight of F(2) pups within the high-dose group but caused no effects on weaning index and sex ratio. Exposure of ZnCl(2) to F(0) and F(1) parental males resulted in a significant reduction in their body weights, and the F(0) and F(1) parental females did not show any significant difference in their body weights compared to their control groups. However, the postpartum dam weights of both F(0) and F(1) female rats were significantly reduced compared to their controls. Exposure of ZnCl(2) to F(o) and F(1) generation parental rats did not produce any significant change of their clinical signs as well as their clinical pathology parameters, except the alkaline phosphotase (ALK) level, which showed an upward trend in both sexes of both generations. Exposure of ZnCl(2) to F(0) rats resulted in a reduction of brain, liver, kidney, spleen and seminal vesicles weights of males and in the spleen and uterus of females. Similarly, exposure of F(1) rats to ZnCl(2) also resulted in reduction of brain, liver, kidney, adrenal, spleen, prostate and seminal vesicles weights of males and in spleen and uterus of females. ZnCl(2) exposure resulted in grossly observed gastro-intestianla (GI) tract, lymphoreticular/hematopoietic, and reproductive tract lesions in parental rats in both generations. Reduced body fat was also recorded in F(1) parental rats.     

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.     

Effect of pre-treatment and supporting media on Ni(II), Cu(II), Al(III) and Fe(III) sorption by plant root material

In this work Paspalum notatum root material was used to elucidate the influence of acid leaching pre-treatment and of sorption medium on metal adsorption. Ground P. notatum root was leached with 0.14M HNO(3). Leached root material (LRM) and non-leached root material (NLRM) were employed to flow sorption of Ni(II), Cu(II), Al(III) and Fe(III) in 0.5M CH(3)COONH(4) medium at pH 6.5. For LRM the sorption was also studied in 0.5M KNO(3) medium. The acid pre-treatment increased the sorption capacity (SC) for all ions studied. For the KNO(3) medium, Cu(II) and Fe(III) sorption was higher than in CH(3)COONH(4) and the type of the Ni(II) isotherm's model changed. The Freundlich model was the most representative isotherm model to describe metallic ions sorption. The (1)H NMR spectra showed differences between LRM and NLRM and the acid-basic potentiometric titration elucidated that acid-leaching procedure affected the root material sorption sites once only two predominant sorption sites were found for LRM (phenolic and amine, both able cations sorption) and five sorption sites (two carboxylic, amine and two phenolic) were founded for NLRM.     

Bio-reduction of arsenate using a hydrogen-based membrane biofilm reactor

Arsenate (As(V)) is a carcinogen and a significant problem in groundwater in many parts of the world. Since As(III) is generally more mobile and more toxic than As(V), the reduction of As(V) to As(III) is not a conventional treatment goal. However, reducing As(V) to As(III) may still be a means for decontamination, because As(III) can be removed from solution by precipitation or complexation with sulfide or by adsorption to Fe(II)-based solids. A promising approach for reducing oxidized contaminants is the H2-based membrane biofilm reactor (MBfR). In the case of arsenate, the MBfR allows bio-reduction of As(V) to As(III) and sulfate to sulfide, thereby giving the potential for As removal, such as by precipitation of As2S3(s) or formation of Fe(II)-based solids. When As(V) was added to a denitrifying MBfR, As(V) was reduced immediately to As(III). Decreasing the influent sulfate loading increased As(V) reduction for a fixed H2 pressure. A series of short-term experiments elaborated on how As(V) loading, nitrate and sulfate loadings, and H2 pressure controlled As(V) reduction. Lower nitrate loading and increased As(V) loading increased the extent of As(V) reduction, but increased H2 pressure did not increase As(V) reduction. As(V) reduction was sensitive to sulfate loading, with a maximum As(V)-removal percentage and flux with no addition of sulfate. As(III) could be precipitated with sulfide or adsorbed to Fe(II) solids, which was verified by scanning electron microscopy and energy dispersive X-ray analysis.     

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.     

Mechanistic and kinetic study on the ozonolysis of n-butyl vinyl ether, i-butyl vinyl ether and t-butyl vinyl ether

Density functional theory (DFT) and ab initio method are employed to elucidate the mechanisms for O(3)-initiated oxidation of n-butyl vinyl ether (n-BVE) and its isomers (i-BVE and t-BVE). For each BVE, the reactions proceed via O(3) cycloaddition resulting in the formation of primary ozonides (POZs) and then two self-decomposition pathways of POZs are followed. Major products are identified to be formaldehyde and butyl formates (CH(3)CH(2)CH(2)CH(2)OCHO for n-BVE, (CH(3))(2)CHCH(2)OCHO for i-BVE and (CH(3))(3)COCHO for t-BVE). The total and individual rate constants for main product channels have been calculated using the modified multichannel Rice-Ramsperger-Kassel-Marcus (RRKM) approach. At 298 K and 101 kPa, the calculated total rate constants are 2.50×10(-16), 3.41×10(-16) and 4.17×10(-16) cm(3) molecule(-1) s(-1) for n-BVE+O(3), i-BVE+O(3) and t-BVE+O(3), respectively, which are in perfect agreement with experimental results. The total rate coefficients are almost pressure independent in the range of 0.001-101 kPa but obviously positive temperature dependent over the whole study temperature range (200-400 K). Also, the favorable reaction pathways have been determined through the estimation of branching ratios. Moreover, the influence of alkoxy group structure on the reactivity of vinyl ethers was examined.     

Distribution of fission products in dust samples from the region of Thessaloniki, Greece, after the Chernobyl nuclear accident

The distribution of the fission products (95)Zr, (95)Nb, (103)Ru, (106)Ru (determined through (106)Rh), (125)Sb, (129m)Te, (134)Cs, (137)Cs, (140)Ba, (140)La, (141)Ce and (144)Ce has been determined in dust samples from the region of Thessaloniki, Greece, after the nuclear accident at Chernobyl. The samples studied also included (110m)Ag, not belonging to the products of (235)U fission. Samples showing higher concentrations of radionuclides also show a higher content in clay minerals, whereas samples having low concentrations of radionuclides usually contain large amounts of quartz and feldspars. Desorption and leaching experiments using solutions of chlorides of sodium, potassium, calcium and magnesium (0.5 N), as well as distilled and tap water, were also performed. Sodium and potassium chloride solutions were found to be efficient in desorbing and/or leaching of caesium and ruthenium isotopes to an extent of about 30%.     

Using FeGAC/H2O2 process for landfill leachate treatment

Due to the growing concern of highly contaminated landfill leachate problems in Taiwan, an innovative advanced catalytic oxidation (FeGAC/H(2)O(2)) process was developed and employed in this research to treat the landfill leachate from central Taiwan. Experimental results indicated that the FeGAC/H(2)O(2) process could effectively remove organic compounds from landfill leachate. The presence of iron oxide coated granular activated carbon (FeGAC) greatly improved the oxidative ability of H(2)O(2) for the removal of humic acids, fulvic acids and non-humic substance from leachate. For instance, at pH 6, the removal efficiencies of FeGAC/H(2)O(2) and H(2)O(2) processes were 70% and 8%, respectively. FeGAC/H(2)O(2) combined both advantages of FeGAC and H(2)O(2) where FeGAC had good organics adsorption ability and could effectively catalyse the hydrogen peroxide oxidation reaction for organics removal.