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.     

Diminution of migration of phthalic acid esters in tequila beverage by the year of production

Abstract

The presence of diethyl-phthalate (DEP), dibutyl-phthalate (DBP), butylbenzyl-phthalate (BBP), diethylhexyl-phthalate (DEHP) and diisononyl-phthalate (DINP) was determined in 295 tequila samples. They were grouped by age of maturation (white, aged, extra aged or ultra aged) and year of production (between 2013 and 2018). Gas Chromatography coupled with Mass Spectrometry was used for identification and quantification. The results showed that 65 samples (22% of the total) were phthalate free. DEP (0.13-0.27?mg/kg), BBP (0.05–2.91?mg/kg) and DINP (1.64–3.43?mg/kg) were detected in 11 (3.73%), 37 (12.54%) and 5 (1.69%) samples, respectively. But, these concentrations did not exceed the maximum permitted limits (MPL) of phthalates for alcoholic beverages. DBP (0.01–2.20?mg/kg) and DEHP (0.03–4.64?mg/kg) were detected in 96 (32.54%) and 224 (75.93%) samples, from them only 10 (3.39%) and 15 (5.08%) samples, respectively, exceeded the MPL for alcoholic beverages and they were few tequilas produced in the year 2014 or before. DEHP was the most frequent phthalate found in tequila and observed DEHP concentrations were 2-times higher in ultra aged tequilas compared to those in white tequilas. We concluded that all tequilas produced in 2015 and after, satisfied the international standards for these compounds.     

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.     

Estrogenic and thyroid hormone activity of a series of hydroxy-polychlorinated biphenyls

A series of novel synthetic monohydroxy polychlorinated biphenyls (OH-PCBs) (5 trichloro-, 5 tetrachloro- and 5 pentachloro-compounds) have been characterized (1H and 13C NMR and high resolution MS) and their estrogenic and thyroid hormone activities assessed using a yeast two-hybrid assay, both with and without possible metabolic activation by rat liver S9 preparation. Moderate estrogenic activity was found for 2,3,4(')-trichlorobiphenyl-4-ol (compound 5) but this was eliminated when exposed to the S9 mix. 2,2('),3('),4,6-Pentachlorobiphenyl-3-ol (13) and 2('),3,3('),6-tetrachlorobiphenyl-4-ol (10) both showed weak estrogenicity in the absence of the S9 mix. The estrogenicity of compound (10) was enhanced 10-fold by exposure to S9 metabolic activation but that of compound (13) remained unchanged. 2('),4,5('),6-Tetrachlorobiphenyl-2-ol (6) showed strong thyroid hormonal activity (5% of that of T4) whereas 3('),4,6-trichlorobiphenyl-3-ol (4), compound (10) and 2,3('),4,5('),6-pentachlorobiphenyl-3-ol (14) showed moderate activity, and 2('),3,3('),5-tetrachlorobiphenyl-2-ol (8) and 3,3('),5,5('),6-pentachlorobiphenyl-2-ol (11) showed weak activity. The activity of (4) was eliminated by S9 metabolic activation whereas those of (6) and (14) were weakened and that of (10) remained unchanged.     

Spectroscopic investigation of magnetite surface for the reduction of hexavalent chromium

The reduction of Cr(VI) to Cr(III) by magnetite in the presence of added Fe(II) was characterized through batch kinetic experiments and the effect of Fe(II) addition and pH were investigated in this study. The addition of Fe(II) into magnetite suspension improved the reductive capacity of magnetite. Eighty percent of Cr(VI) was reduced by magnetite (6.5 g l(-1)) with Fe(II) (80 mg l(-1)) within 1 h, while 60% of Cr(VI) was removed by magnetite only. However, the extent of improved reductive capacity of magnetite with Fe(II) was less than that predicted by the summation of each reduction capacity of magnetite and Fe(II). The reduction of Cr(VI) in the magnetite suspension with Fe(II) increased with the increase of molar ratio of Fe(II) to Cr(VI) (0.6, 1, 1.5, 2.3) in the range of 0-2.3 and with the decrease of pH in the range of pH 8.0-5.5. The speciation of chromium, iron, and oxygen on the surface of magnetite was investigated by X-ray photoelectron spectroscopy. Cr 2p3/2, Fe 2p3/2, and O 1s peaks were mainly observed at 576.7 and 577.8 eV, at 711.2 eV, and at 530.2 and 531.4 eV, respectively. The results indicates that Cr(III) and Fe(III) were the dominant species on the surface of magnetite after reaction and that the dominant species covered the magnetite surface and formed metal (oxy)hydroxide.     

Temperature dependence of Henry's law constants of metolachlor and diazinon

A dynamic system based on the water/air equilibrium at the interface within the length of a microporous tube has been used to determine experimentally the Henry's law constants (HLC) of two pesticides: metolachlor and diazinon. The measurements were conducted over the temperature range 283-301 K. At 293 K, HLCs values are (42.6+/-2.8) x 10(3) (in units of M atm(-1)) for metolachlor and (3.0+/-0.3)x10(3) for diazinon. The obtained data were used to derive the following Arrhenius expressions: HLC=(3.0+/-0.4) x 10(-11) exp((10,200+/-1,000)/T) for metolachlor and (7.2+/-0.5) x 10(-15) exp((11,900+/-700)/T) for diazinon. At a cumulus cloud temperature of 283 K, the fractions of metolachlor and diazinon in the atmospheric aqueous phase are about 57% and 11% respectively. In order to evaluate the impact of a cloud on the atmospheric chemistry of both studied pesticides, we compare also their atmospheric lifetimes under clear sky (tau(gas)), and cloudy conditions (tau(multiphase)). The calculated multiphase lifetimes (in units of hours) are significantly lower than those in gas phase at a cumulus temperature of 283 K (in parentheses): metolachlor, 0.4 (2.9); diazinon, 1.9 (5.0).     

Performance of the supported copper oxide catalysts for the catalytic incineration of aromatic hydrocarbons

A fixed bed reactor was used to assess the catalytic incineration of toluene by various transition-metal oxide species supported on gamma-Al(2)O(3). CuO/gamma-Al(2)O(3) was found to be the most active of seven catalysts investigated. The CuO species, with a Cu content of 5% (wt), was hence used with four different supports (CeO(2), gamma-Al(2)O(3), TiO(2) and V(2)O(5)) in order to define the optimal combination. Results of the catalytic incineration of toluene, X-ray diffraction (XRD) analysis, oxygen-temperature programmed desorption (O(2)-TPD), toluene-temperature programmed desorption (toluene-TPD) and hydrogen-temperature programmed reduction (H(2)-TPR) showed that CuO/CeO(2) was the most active catalyst, followed by CuO/gamma-Al(2)O(3). The activity of CuO/CeO(2) with respect to the VOC molecule was observed to follow this sequence: toluen>p-xylene>benzene. The addition of water vapor or CO(2) significantly inhibited the activity of the CuO/CeO(2) and CuO/gamma-Al(2)O(3) catalysts. The inhibiting effect of both was reversible for CuO/gamma-Al(2)O(3). For CuO/CeO(2), the inhibiting effect of CO(2) was reversible and even insignificant at a higher temperature (220 degrees C), but the effect of H(2)O vapor was somewhat irreversible at lower incineration temperatures (220 degrees C). For complete oxidation of toluene, the required reaction temperature increased with gas hourly space velocity (GHSV) and toluene inlet concentration.     

The evaluation of stability during the composting of different starting materials: comparison of chemical and biological parameters

Three blends formed by: (i) food processing waste (CP(FP)), (ii) waste water sewage sludge (CP(WW)), and (iii) their mixture (CP(FP+WW)), blended with tree pruning as bulking agent, were composted over 3 months. During composting the blends were monitored for the main physical-chemical characteristics: temperature, oxygen saturation level (O(2)%), pH, total and volatile solids, total organic carbon, and organic nitrogen (N(org)). In addition to the main parameters, the dissolved organic carbon (DOC), the inorganic nitrogen and the Oxygen Uptake Rate (OUR) were monitored. All the mixtures easily reached a peak temperature around 70°C, related to the lowest O(2)%. After 90 d, CP(FP), CP(FP+WW), and CP(WW) showed an organic matter mineralization of 43%, 35% and 33%, respectively; CP(FP) fitted an exponential model while both CP(FP+WW), and CP(WW) fitted a logistic model. During composting an OUR reduction of 79%, 78% and 73% was registered in CP(FP), CP(FP+WW), and CP(WW), respectively; the OUR successfully fitted the adopted exponential model and well reflected the stabilization process in time. The N(org) recovery at the end of the process was positive only in CP(WW) (11.6%). The DOC significantly decreased during the composting process but did not successfully fit any model. The mineral nitrogen did not follow the typical pattern with NH(4)(+) disappearance and NO(3)(-) accumulation. Strong NO(3)(-) losses were evident in all blends, while NH(4)(+) accumulations were detectable only in CP(FP), and CP(FP+WW). The NH(4)(+)/NO(3)(-) ratio did not satisfactorily reflect the composting process over time. The comparison of the first order (exponential) and logistic (sigmoidal) models applied to the OUR and OM course highlights the role of mineral nitrogen as limiting factor during composting of the more stabilized sludge.     

Effect of pencycuron on microbial parameters of waterlogged soil

A laboratory study was conducted to monitor the effect of pencycuron [1-(4-chlorobenzyl)-1-cyclopentyl-3-phenylurea] on microbial parameters of alluvial (AL) soil (Typic udifluvent) and coastal saline (CS) soil (Typic endoaquept) under waterlogged condition. Pencycuron at field rate (FR), 2FR and 10FR affected the microbial biomass C (MBC), soil ergosterol content and fluorescein diacetate hydrolyzing activity (FDHA) differentially. The DCM amendment did not seem to have any counteractive effect on the toxicity of pencycuron on the microbial variables. The change in microbial metabolic quotient (qCO2) and microbial respiration quotient (QR), indicated pencycuron induced disturbance at 10FR. Present study revealed that the metabolically activated microbial population was more suppressed compared to the dormant population.     

Impact of pH buffer capacity of sediment on dechlorination of atrazine using zero valent iron

This research investigated the role of the pH buffer capacity of sediment on the dechlorination of atrazine using zero valent iron (ZVI). The buffer capacity of the sediment was quantified by batch experiments and estimated to be 5.0 cmol OH(-) . pH(-1). The sediments were spiked with atrazine at 7.25-36.23 mg kg(-1) (6.21 x 10(-7)-3.09 x 10(-6) mol atrazine . g(-1) sediment) for the batch experiments. The buffer capacity of the sediment maintained the sediment suspension at neutral pH, thereby enabling continuous dechlorination until the buffer capacity of the sediment was depleted. The pseudo-first order dechlorination constants were estimated to be in the range of 1.19 x 10(-2)-7.04 x 10(-2) d(-1) for the atrazine-spiked sediments.     

Effect of Fe (III) on acid degradation of methylparathion

A study was undertaken to determine the transformation kinetic of methylparathion (O, O, -dimethyl O-4 nitrophenylphosphorotioate) in the presence of Fe(III) between pH 2 and 7. The Fe(III) was not electroactive under the conditions used in this study, and polarographic signals were exhibited by methylparathion and main degradation product only. Data suggest that hydrolysis of methylparathion in an acid medium is catalyzed by Fe(III) and the pesticide did not degrade in this medium without this cation. Methylparathion degradation was observed at all the pHs studied and was independent of the predominant chemical form of Fe(III) in the aqueous medium. The reaction was first-order with pH-dependent rate constant (k) values ranging from 3.3 x 10(- 3) h(- 1) to 7.0 x 10(- 3) h(- 1). The k values increased as pH decreased, suggesting that Fe(III) acted as an electrophile in the reaction mechanism.     

Effect of some xenobiotics on kynurenine hydrolase and kynurenine aminotransferase of mouse liver

Abstract

The effects of some xenobiotics on the activity of the B₆‐dependent kynurenine hydrolase (KH) and kynurenine aminotransferase (KATE) in mouse liver, were investigated. Polychlorinated biphenyl (Aroclor 1254) (400mg/kg/day ×4) markedly decreased the activity of both enzymes. Benzo(a)pyrene (BP) and 3‐methylcholanthrene (3‐MC) (40mg/Kg/day ×1) as well as phénobarbital (PB) (75mg/kg/day ×3) did not alter the activity of KH, while that of KATE was mildy reduced. The response of the two enzymes to treatment with chlorpromazine (CPZ) (5mg/Kg/day ×5) were opposite with marked elevation of KH and inhibition of KATE activities. Treatment with B‐naphthoflavone (B‐NF) (80mg/Kg/day ×2), Pyrazole (200mg/Kg/day ×1) or indole (400mg/kg/day ×1) produce no change in the activity of either enzyme. It, seems therefore, that Aroclor(1254) and chlorpromazine may cause disordered kynurenine metabolism through alterations in the activities of its metabolizing enzymes. This, in turn, might affect nicotinamide adenine dinucleotide biosynthesis and/or the accumulation of some tryptophan metabolites suspected of being carcinogenic or co‐carcinogenic.     

Kinetic assessment of the potassium ferrate(VI) oxidation of antibacterial drug sulfamethoxazole

Sulfamethoxazole (SMX), a worldwide-applied antibacterial drug, was recently found in surface waters and in secondary wastewater effluents, which may result in ecotoxical effects in the environment. Herein, removal of SMX by environmentally-friendly oxidant, potassium ferrate(VI) (K(2)FeO(4)), is sought by studying the kinetics of the reaction between Fe(VI) and SMX as a function of pH (6.93-9.50) and temperature (15-45 degrees C). The rate law for the oxidation of SMX by Fe(VI) is first-order with respect to each reactant. The observed second-order rate constant decreased non-linearly from 1.33+/-0.08 x 10(3) M(-1)s(-1) to 1.33+/-0.10 x 10(0) M(-1)s(-1) with an increase of pH from 7.00 to 9.50. This is related to protonation of Fe(VI) (HFeO(4)(-) <==> H(+) + FeO(4)(2-); pK(a,HFeO(4)) = 7.23) and sulfamethoxazole (SH <==> H(+) + S(-); pK(a,SH)=5.7). The estimated rate constants were k(11)(HFeO(4)(-) + SH) = 3.0 x 10(4) M(-1)s(-1), k(12)(HFeO(4)(-) + S(-)) = 1.7 x 10(2) M(-1)s(-1), and k(13) (FeO(4)(2-) + SH) = 1.2 x 10(0) M(-1)s(-1). The energy of activation at pH 7.0 was found to be 1.86+/-0.04 kJ mol(-1). If excess potassium ferrate(VI) concentration (10 microM) is used than the SMX in water, the half-life of the reaction using a rate constant obtained in our study would be approximately 2 min at pH 7. The reaction rates are pH dependent; thus, so are the half-lives of the reactions. The results suggest that K(2)FeO(4) has the potential to serve as an oxidative treatment chemical for removing SMX in water.     

Effect of some xenobiotics on kynurenine hydrolase and kynurenine aminotransferase of mouse liver

The effects of some xenobiotics on the activity of the B6-dependent kynurenine hydrolase (KH) and kynurenine aminotransferase (KATE) in mouse liver, were investigated. Polychlorinated biphenyl (Aroclor 1254) (400mg/kg/day x4) markedly decreased the activity of both enzymes. Benzo(a)pyrene (BP) and 3-methylcholanthrene (3-MC) (40mg/Kg/day x1) as well as phenobarbital (PB) (75mg/kg/day x3) did not alter the activity of KH, while that of KATE was mildy reduced. The response of the two enzymes to treatment with chlorpromazine (CPZ) (5mg/Kg/day x5) were opposite with marked elevation of KH and inhibition of KATE activities. Treatment with B-naphthoflavone (B-NF) (80mg/Kg/day x2), Pyrazole (200mg/Kg/day x1) or indole (400mg/kg/day x1) produce no change in the activity of either enzyme. It, seems therefore, that Aroclor (1254) and chlorpromazine may cause disordered kynurenine metabolism through alterations in the activities of its metabolizing enzymes. This, in turn, might affect nicotinamide adenine dinucleotide biosynthesis and/or the accumulation of some tryptophan metabolites suspected of being carcinogenic or co-carcinogenic.     

Effect of coumaphos on cholinesterase activity, hematology, and biochemical blood parameters of bovines in tropical regions of Mexico

To assess the effect of coumaphos [O-(3-chloro-4-methyl-2-oxo-2H-1-benzopyran-7-yl) O,O-diethyl phosphorothioate] exposure on physiological responses during bovine production, acetylcolinesterase (AChE) and butyrylcholinesterase (BuChE) activities were measured in whole blood, erythrocytes, and plasma of healthy male steers (Bos Taurus x Bos indicus) sprayed with coumaphos at a non-lethal dose of 1 mg kg(- 1) body weight per day once every 14 (in vivo group) or 21 days (southern and central groups). Coumaphos topically administered at 1 mg/kg body weight per day to cattle under normal management practices in tropical areas produced a significant inhibition in erythrocyte (RBC) AChE and BuAChE activities when compared to baseline levels. RBC-AChE activity for the in vivo group decreased 71.3% (P < 0.05) and BuChE activity 59.1% (P < 0.05); RBC-AChE activity decreased 55.1% (P < 0.05) (southern group) and 43.4% (P < 0.05) (central group). Compared to the control specimens, steers from in vivo, southern, and central groups after 150 days of exposure had lower (P < 0.05) leukocyte count, absolute lymphocyte, erythrocyte, and platelet counts. Decreases in RBC-AChE activities correlated with decreased lymphocyte (r = 1.000, p = 0.01), erythrocyte (r = 1.000, p = 0.003), and platelet counts (r = 0.841, p = 0.036). Significantly increased BUN levels (P < 0.05) correlated with the decrease in RBC-AChE activities (r = - 0.997, p = 0.047) and with the decrease in absolute red blood cell (r = - 0.883, p = 0.020) and lymphocyte (r = - 0.825, p = 0.043) counts; increased (P < 0.05) total plasma protein levels correlated with the decrease in RBC-AChE activities (r = -0.998, p = 0.043), absolute red blood cell (r = - 0.998, p = 0.040), lymphocyte (r = - 0.893, p = 0.017), and platelet (r = -0.855, p = 0.030) counts. The physiological responses correlated with the erythrocyte acetylcholinesterase inhibition could be considered as early indicators or warning responses of bovine exposures to organophosphorus pesticides (OPs).     

Development of a multi-factor model for predicting the effects of ambient ozone on the biomass of white clover

Results are presented from the UN/ECE ICP Vegetation (International Cooperative Programme on effects of air pollution on natural vegetation and crops) experiments in which ozone(O(3))-resistant (NC-R) and -sensitive (NC-S) clones of white clover (Trifolium repens cv. Regal) were exposed to ambient O(3) episodes at 14 sites in eight European countries in 1996, 1997 and 1998. The plants were grown according to a standard protocol, and the forage was harvested every 28 days for 4-5 months per year by excision 7 cm above the soil surface. Biomass ratio (NC-S/NC-R) was related to the climatic and pollutant conditions at each site using multiple linear regression (MLR) and artificial neural networks (ANNs). Twenty-one input parameters [e.g. AOT40, 7-h mean O(3) concentration, daylight vapour pressure deficit (VPD), daily maximum temperature] were considered individually and in combination with the aim of developing a model with high r(2) and simple structure that could be used to predict biomass change in white clover. MLR models were generally more complex, and performed less well for unseen data than non-linear ANN models. The ANN model with the best performance had five inputs with an r(2) value of 0.84 for the training data, and 0.71 for previously unseen data. Two inputs to the model described the O(3) conditions (AOT40 and 24-h mean for O(3)), two described temperature (daylight mean and 24-h mean temperature), and the fifth input appeared to be differentiating between semi-urban and rural sites (NO concentration at 17:00). Neither VPD nor harvest interval was an important component of the model. The model predicted that a 5% reduction in biomass ratio was associated with AOT40s in the range 0.9-1.7 ppm x h (microl l(-1) h) accumulated over 28 days, with plants being most sensitive in conditions of low NO(x), medium-range temperature, and high 24-h mean O(3) concentration.     

Influence of complex reagents on removal of chromium(VI) by zero-valent iron

The removal of Cr(VI) by zero-valent iron (Fe(0)) and the effect of three complex reagents, ethylenediaminetetraacetic acid (EDTA), NaF and 1,10-phenanthroline, on this reaction were investigated using batch reactors at pH values of 4, 5 and 6. The results indicate that the removal of Cr(VI) by Fe(0) is slow at pH 5.0 and that three complex reagents play different roles in the reaction. EDTA and NaF significantly enhance the reaction rate. The zero-order rate constants at pH 5.0 were 5.44 microM min(-1) in the presence of 4mM EDTA and 0.99 micrM min(-1) in the presence of 8 mM NaF, respectively, whereas that of control was only 0.33 micrM min(-1), even at pH=4.0. This enhancement is attributed to the formation of complex compounds between EDTA/NaF and reaction products, such as Cr(III) and Fe(III), which eliminate the precipitates of Cr(III), Fe(III) hydroxides and Cr(x)Fe(1-)(x)(OH)(3) and thus reduce surface passivation of Fe(0). In contrast, 1,10-phenanthroline, a complex reagent for Fe(II), dramatically decreases Cr(VI) reduction by Fe(0). At pH=4.0, the zero-order rate constant in the presence of 1mM of 1,10-phenanthroline was 0.02 micrM min(-1), decreasing by 99.7% and 93.9%, respectively, compared with the results in the presence and absence of EDTA. The results suggest that a pathway of the reduction of Cr(VI) to Cr(III) by Fe(0) may involve dissolution of Fe(0) to produce Fe(II), followed by reduction of Cr(VI) by Fe(II), rather than the direct reaction between Cr(VI) and Fe(0), in which Fe(0) transfers electrons to Cr(VI).     

Adsorption of molybdate and tetrathiomolybdate onto pyrite and goethite: effect of pH and competitive anions

The adsorption of two major molybdenum (Mo) species, molybdate (MoO4(2-)) and tetrathiomolybdate (MoS4(2-)) onto two main iron minerals pyrite (FeS2) and goethite (FeOOH) is addressed to elucidate the possible mechanisms of molybdenum immobilization in anoxic sediments. Suspensions of MoS4(2-) (or MoO4(2-)) and goethite (or pyrite) in 0.1M NaCl solution were equilibrated under anoxic conditions at 25 degrees C in the pH range from 3 to 10. The competitive effects of sulfate, phosphate, and silicate on the adsorption of MoO4(2-) and MoS4(2-) by pyrite and goethite are also addressed. Adsorption of MoO4(2-) and MoS4(2-) on pyrite and goethite is in general well described by a Langmuir model at low pH; the extent of sorption is a function of pH and the surface loading. Maximum sorption is observed in the acidic pH range (pH<5) at low surface loading. The adsorption of molybdenum (micromol g(-1)) depends upon Mo species and on the type of iron mineral following the order: MoS4(2-)-goethite > MoO4(2-)-goethite > MoS4(2-)-pyrite > MoO4(2-)-pyrite. Phosphate appears to compete strongly with MoO4(2-) and MoS4(2-) for the sorption sites of pyrite and goethite. The strength of the phosphate competitive effect follows the sequence of MoO4(2-)-goethite approximately = MoO4(2-)-pyrite > MoS4(2-)-pyrite > MoS4(2-)-goethite. Silicate and sulfate have a negligible effect on the sorption of MoO4(2-) and MoS4(2-). The preferred adsorption by iron mineral of MoS4(2-), as well as its behavior in the presence of competitive anions suggests that tetrathiomolybdate species may be an ultimate reservoir and may control Mo enrichment in the sediments.     

Catalytic decomposition of hydrogen peroxide and 4-chlorophenol in the presence of modified activated carbons

The objective of this research was to examine the heterogeneous catalytic decomposition of H(2)O(2) and 4-chlorophenol (4-CP) in the presence of activated carbons modified with chemical pretreatments. The decomposition of H(2)O(2) was suppressed significantly by the change of surface properties including the decreased pH(pzc) modified with oxidizing agent and the reduced active sites occupied by the adsorption of 4-CP. The apparent reaction rate of H(2)O(2) decomposition was dominated by the intrinsic reaction rates on the surface of activated carbon rather than the mass transfer rate of H(2)O(2) to the solid surface. By the detection of chloride ion in suspension, the reduction of 4-CP was not only attributed to the advanced adsorption but also the degradation of 4-CP. The catalytic activity toward 4-CP for the activated carbon followed the inverse sequence of the activity toward H(2)O(2), suggesting that acidic surface functional group could retard the H(2)O(2) loss and reduce the effect of surface scavenging resulting in the increase of the 4-CP degradation efficiency. Few effective radicals were expected to react with 4-CP for the strong effect of surface scavenging, which could explain why the degradation rate of 4-CP observed in this study was so slow and the dechlorination efficiency was independent of the 4-CP concentration in aqueous phase. Results show that the combination of H(2)O(2) and granular activated carbon (GAC) did increase the total removal of 4-CP than that by single GAC adsorption.