PTR-MS measurement of partition coefficients of reduced volatile sulfur compounds in liquids from biotrickling filters

Biological air filtration for reduction of emissions of volatile sulfur compounds (e.g., hydrogen sulfide, methanethiol and dimethyl sulfide) from livestock production facilities is challenged by poor partitioning of these compounds into the aqueous biofilm or filter trickling water. In this study, Henry’s law constants of reduced volatile sulfur compounds were measured for deionized water, biotrickling filter liquids (from the first and second stages of a two-stage biotrickling filter), and NaCl solutions by a dynamic method using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) at a temperature range of 3–45 °C. NaCl solutions were used to estimate salting-out constants up to an ionic strength of 0.7 M in order to evaluate the effect of ionic strength on partitioning between air and biofilter liquids. Thermodynamic parameters (enthalpy and entropy of phase exchange) were obtained from the measured partition coefficients as a function of temperature. The results show that the partition coefficients of organic sulfur compounds in the biotrickling filter liquids were generally very close to the corresponding partition coefficients in deionized water. Based on the estimated ionic strength of biofilter liquids, it is assessed that salting-out effects are of no importance for these compounds. For H₂S, a higher enthalpy of air–liquid partitioning was observed for 2nd stage filter liquid, but not for 1st stage filter liquid. In general, the results show that co-solute effects for sulfur compounds can be neglected in numerical biofilter models and that the uptake of volatile sulfur compounds in biotrickling filter liquids cannot be increased by decreasing ionic strength.     

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.     

Assessment of five bioaccessibility assays for predicting the efficacy of petroleum hydrocarbon biodegradation in aged contaminated soils

In this study, the bioaccessibility of petroleum hydrocarbons in aged contaminated soils (1.6-67gkg(-1)) was assessed using four non-exhaustive extraction techniques (100% 1-butanol, 100% 1-propanol, 50% 1-propanol in water and hydroxypropyl-β-cyclodextrin) and the persulfate oxidation method. Using linear regression analysis, residual hydrocarbon concentrations following bioaccessibility assessment were compared to residual hydrocarbon concentrations following biodegradation in laboratory-scale microcosms in order to determine whether bioaccessibility assays can predict the endpoint of hydrocarbon biodegradation. The relationship between residual hydrocarbon concentrations following microcosm biodegradation and bioaccessibility assessment was linear (r(2)=0.71-0.97) indicating that bioaccessibility assays have the potential to predict the extent of hydrocarbon biodegradation. However, the slope of best fit varied depending on the hydrocarbon fractional range assessed. For the C(10)-C(14) hydrocarbon fraction, the slope of best fit ranged from 0.12 to 0.27 indicating that the non-exhaustive or persulfate oxidation methods removed 3.5-8 times more hydrocarbons than biodegradation. Conversely, for the higher molecular weight hydrocarbon fractions (C(29)-C(36) and C(37)-C(40)), biodegradation removed up to 3.3 times more hydrocarbons compared to bioaccessibility assays with the resulting slope of best fit ranging from 1.0-1.9 to 2.0-3.3 respectively. For mid-range hydrocarbons (C(15)-C(28)), a slope of approximately one was obtained indicating that C(15)-C(28) hydrocarbon removal by these bioaccessibility assays may approximate the extent of biodegradation. While this study demonstrates the potential of predicting biodegradation endpoints using bioaccessibility assays, limitations of the study include a small data set and that all soils were collected from a single site, presumably resulting from a single contamination source. Further evaluation and validation is required using soils from a range of hydrocarbon contamination sources in order to develop robust assays for predicting bioremediation endpoints in the field.     

A laser flash photolysis study of the decay of SO4- and Cl2- radical anions in the presence of Cl- in aqueous solutions

The rate constant for the reaction of sulphate radical (SO4-) with Cl- has been determined using laser photolysis, at 248 nm, of peroxodisulphate anions to produce the radicals and time resolved optical absorption of the transient species (at 450 or 480 nm for SO4- and 350 nm for Cl2-) for the kinetic determinations. The experiments were performed, in the absence of added sulphate, as a function of temperature and ionic strength and yielded (at an ionic strength of 0.0157 M): kIV = (9.90+/-0.16) x 10(9) exp((-7.12+/-2.0) kJ mol(-1)/RT) M(-1) s(-1), where the errors reflect the 2sigma statistical error. This reaction produces Cl2-, the formation and decay of which were also monitored allowing a determination of the rate constant of its second-order self-recombination reaction which gave k = (6.50+/-1.40) x 10(8) M(-1) s(-1) at 293 K and zero ionic strength.     

Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE)

The kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE) in aqueous solutions at various pH, temperature, oxidant concentration and ionic strength levels was studied. The MTBE degradation was found to follow a pseudo-first-order decay model. The pseudo-first-order rate constants of MTBE degradation by persulfate (31.5 mM) at pH 7.0 and ionic strength 0.11 M are approximately 0.13 x 10(-4), 0.48 x 10(-4), 2.4 x 10(-4) and 5.8 x 10(-4) S(-1) at 20, 30, 40 and 50 degrees C, respectively. Under the above reaction conditions, the reaction has an activation energy of 24.5 +/- 1.6 kcal/ mol and is influenced by temperature, oxidant concentration, pH and ionic strength. Raising the reaction temperature and persulfate concentration may significantly accelerate the MTBE degradation. However, increasing both pH (over the range of 2.5-11) and ionic strength (over the range of 0.11-0.53 M) will decrease the reaction rate. Reaction intermediates including tert-butyl formate, tert-butyl alcohol, acetone and methyl acetate were observed. These intermediate compounds were also degraded by persulfate under the experimental conditions. Additionally, MTBE degradation by persulfate in a groundwater was much slower than in phosphate-buffer solutions, most likely due to the presence of bicarbonate ions (radical scavengers) in the groundwater.     

Factors affecting biosurfactant production by oil degrading Aeromonas spp. isolated from a tropical environment

An Aeromonas spp. was isolated from tropical estuarine water. The organism grew on crude oil and produced biosurfactant that could emulsify hydrocarbons. The peak growth and biosurfactant production was on the 8th day. The organism grew on a range of hydrocarbons that include crude oil and hexadecane while no growth was recorded on some hydrocarbons that include benzene. The biosurfactant produced by the organism emulsified a range of hydrocarbons with diesel (E24=65) as the best substrate and hexane (E24=22) as the poorest. After purification, the biosurfactant was found to contain about 38% carbohydrate and an unidentified lipid. No protein was present in the purified biosurfactant. Production of biosurfactant was highest in medium with glucose and lowest in the medium with diesel+acetate. Soybean was the best nitrogen source for biosurfactant production. The activity of the biosurfactant was enhanced optimally at NaCl concentration of 5%, pH of 8.0 and temperature of 40 degrees C. The biosurfactant retained 77% of its original activity after 120 min of exposure to heat at a temperature of 100 degrees C. Biosurfactant may be produced with this organism using non-hydrocarbon substrates such as glucose and soybean that are readily available and would not require extensive purification for use in food and pharmaceutical industries.     

Electrochemical or UV-photochemical oxidation of industrial wastes containing polar aromatic sulphonates

BACKGROUND AND INTENTION: Aromatic sulphonates other than surfactants and their hydroxy and amino-derivatives are important intermediates for the production of azo dyes. Their production on a large scale can be detrimental for the environment, if the by-products of their synthesis are not disposed of appropriately. An industrial waste, the organic components of which were mainly amino and hydroxy-substituted aromatic sulphonates, seriously endangers the environment close to an dismissed Italian industrial site. Inorganic sulphates and chlorides contained in the waste seriously hinder its disposal by incineration, since they corrode furnace walls. In this work, preliminary exploration of aqueous-phase electrochemically and photochemically induced oxidation techniques have been performed as possible alternatives to incineration. METHODS: Electrochemically-induced oxidation was experimented on individual aromatic sulphonates and on an industrial waste by electrolysing them between smooth platinum electrodes at low temperature (5 degrees C) and high current densities (0.4 A/cm2) with aqueous 0.5 M NaHSO4 electrolyte. Photochemically-induced oxidation was performed by irradiating individual aromatic sulphonates or industrial waste with a 500 W mercury lamp in the presence of sodium peroxydisulphate. RESULTS AND DISCUSSION: After 200 min electrodegradation, 90% of the original compounds disappeared, while 50% Total Organic Carbon (TOC) of an industrial waste was removed from solution after 10 hours. After 180 min UV-photodegradation, 90% of two test aromatic sulphonates disappeared, while 65% of TOC of industrial waste was removed after 5 hours. CONCLUSIONS: Two methods, electrochemical and UV-persulphate oxidation of an industrial waste, were used in order to propose a disposal procedure alternative to incineration. Electrodegradation with smooth Pt anode in 0.5 M NaHSO4 at 5 degrees C halved TOC concentration within 10 hours, while persulphate-assisted UV-photochemical oxidation with a 500 W high pressure Hg lamp abated two-thirds of TOC concentration after 5 hours. Energetic consumption of electrodegradation was 0.33 kWh/g TOC, while that of photooxidation was larger than 2 kWh/g TOC. Although both techniques can be considered efficient from a purely chemical point of view, since both are capable of wet-oxidising the aromatic sulphonates and the industrial waste, electrodegradation seems more promising than a photochemical degradation if economical considerations are also taken into account. Considering also that neither cell design nor catalyst were optimised in this preliminary study, the energy yield of electrodegradation seems likely to be largely improved.     

Determination of growth rate and yield of nitrifying bacteria by measuring carbon dioxide uptake rate.

Nitrifier growth parameters--the maximum growth rate (microAmax) and yield (YA)--were estimated by measuring the rate of carbon dioxide uptake and additional rates of oxygen uptake and ammonia (or nitrite) use. Batch tests in a combined titrimetric and offgas analyzer with enriched Nitrobacter and Nitrosomonas cultures and an activated sludge sample were performed. The measured microAmax values for the Nitrobacter and Nitrosomonas cultures were 0.67 +/- 0.03 day(-1) and 0.54 +/- 0.09 day(-1), while the YA values were 0.072 +/- 0.01 g volatile suspended solids (VSS) x g nitrogen (N)(-1) and 0.14 +/- 0.02 gVSS x gN(-1), respectively. For the activated sludge sample, microAmax was observed to increase with pH (microAmax = 0.72 x 3.3(pH-7.1)) over the range 6.8 to 7.1. All microAmax and YA values determined by this method were similar to those previously reported. Compared with other microAmax and YA estimation methods, this method allows for unique microAmax and YA estimations for given conditions from a single experiment.     

Comparison of the effects of variable site temperatures and constant incubation temperatures on the biodegradation of petroleum hydrocarbons in pilot-scale experiments with field-aged contaminated soils from a cold regions site

Temporal atmospheric temperature changes during summers at sub-Arctic sites often cause periodic fluctuations in shallow landfarm and surface soil temperatures. However, little information is available on the effect of site-relevant variations on biodegradation performance in cold climates. This study compares the rate and extents of biodegradation of petroleum hydrocarbons at variable site temperatures (1-10 °C) representative of summers at a sub-Arctic site reported previously with those obtained under a constant average temperature of 6 °C. The biodegradation was evaluated in pilot-scale landfarming experiments with field-aged petroleum-contaminated soils shipped from Resolution Island (61°30′N, 65°00′W), Nunavut, Canada. Under the variable site temperature conditions biodegradation rate constants of semi- (F2) and non-volatile (F3) hydrocarbon fractions were enhanced by over a factor of two during the 60-d experiment, compared to the constant temperature mode. The decrease in total petroleum hydrocarbons (TPH) under the variable site temperature mode was 55% compared to only 19% under the constant average temperature mode. The enhanced biodegradation is attributable to the non-linear acceleration of microbial activity between 4.7 and 10 °C and faster growth of indigenous hydrocarbon-degrading microbial populations. The first-order biodegradation rate constants of 0.018, 0.024 and 0.016 d⁻¹ for TPH, F2 and F3 fractions at the variable site temperature were in agreement with those determined by an on-site experiment at the same site.     

Homogeneous degradation of 1,2,9,10-tetrachlorodecane in aqueous solutions using hydrogen peroxide, iron and UV light

The homogeneous degradation of the polychlorinated n-alkane, 1,2,9,10-tetrachlorodecane (T4C10), was studied in aqueous solutions of hydrogen peroxide, including Fenton and photo-Fenton reaction conditions. All solutions were adjusted to a pH of 2.8 and an ionic strength of 0.1 M NaClO4 prior to photolysis. T4C10 (2 x 10(-6) M) was substantially degraded by the H2O2/UV system (1.0 x 10(-2) M H2O2), with 60% disappearance in 20 min of irradiation in a photoreactor equipped with 300 nm lamps of light intensity 3.6 x 10(-5) Ein L(-1) min(-1) (established by ferrioxalate actinometry). The reaction produced stoichiometric amounts of chloride ion indicating complete dechlorination of the chlorinated n-alkane. T4C10 degraded very slowly under Fenton (Fe2+/H2O2/dark) and Fenton-like (Fe3+/H2O2/dark) conditions. However, when the same solutions were irradiated, T4C10 degraded more rapidly than in the H2O2/UV system, with 61% disappearance in 10 min of exposure. The rapid degradation is related to the enhanced degradation of hydrogen peroxide to oxidizing *OH radicals under photo-Fenton conditions. Degradation was inhibited in both the H2O2/UV and photo-Fenton systems by the addition of KI and tert-butyl alcohol due to *OH scavenging.     

Direct measurement of fugitive emissions of hydrocarbons from a refinery

Refineries are a source of emissions of volatile hydrocarbons that contribute to the formation of smog and ozone. Fugitive emissions of hydrocarbons are difficult to measure and quantify. Currently these emissions are estimated based on standard emission factors for the type and use of equipment installed. Differential absorption light detection and ranging (DIAL) can remotely measure concentration profiles of hydrocarbons in the atmosphere up to several hundred meters from the instrument. When combined with wind speed and direction, downwind vertical DIAL scans can be used to calculate mass fluxes of the measured gas leaving the site. Using a mobile DIAL unit, a survey was completed at a Canadian refinery to quantify fugitive emissions of methane, C2+ hydrocarbons, and benzene and to apportion the hydrocarbon emissions to the various areas of the refinery. Refinery fugitive emissions as measured with DIAL during this demonstration study were 1240 kg/hr of C2+ hydrocarbons, 300 kg/hr of methane, and 5 kg/hr of benzene. Storage tanks accounted for over 50% of the total emissions of C2+ hydrocarbons and benzene. The coker area and cooling towers were also significant sources. The C2+ hydrocarbons emissions measured during the demonstration amounted to 0.17% of the mass of the refinery hydrocarbon throughput for that period. If the same loss were repeated throughout the year, the lost product would represent a value of US$3.1 million/yr (assuming US$40/bbl). The DIAL-measured hourly emissions of C2+ hydrocarbons were 15 times higher than the emission factor estimates and gave a different perspective on which areas of the refinery were the main source of emissions. Methods, such as DIAL, that can directly measure fugitive emissions would improve the effectiveness of efforts to reduce emissions, quantify the reduction in emissions, and improve the accuracy of emissions data that are reported to regulators and the public.     

Microalgae growth using high-strength wastewater followed by anaerobic co-digestion

Integration of algal biofuel production to wastewater anaerobic digestion infrastructure has the potential to increase biogas production, decrease high and variable internal nitrogen loads, and improve sludge digestibility and dewaterability. In this research, two species of microalgae, Spirulina platensis and Chlorella sp., were grown on sludge centrate and a centrate and nitrified wastewater effluent mixture. Harvested algae were co-digested with waste activated sludge (WAS) at varying ratios. High-growth (6.8 g m(-2) x d(-1)), nitrogen (36.5 g m(-3) x d(-1)), and phosphorus (6.5 g m(-3) x d(-1)) uptake rates were achieved with Chlorella on centrate. No growth was observed with S. platensis under the same conditions; however, both organisms grew well on the centrate and effluent mixture. Co-digestion of algae with WAS improved volatile solids reduction. Although co-digestion with S. platensis improved biosolids dewaterability, Chlorella had a slight negative effect on dewaterability compared to WAS alone. The efficiency of energy conversion from photons to biogas generated from Chlorella was estimated at 1.4%.     

Photochemical transformation of azoxystrobin in aqueous solutions

The photochemical behaviour of azoxystrobin fungicide (AZX) in water was studied under laboratory conditions. Photodegradation was initiated using a solar simulator (xenon arc lamp) or a jacketed Pyrex reaction cell equipped with a 125 W, high-pressure mercury lamp. HPLC/MS analysis (APCI and ESI in positive and negative modes) was used to identify AZX photoproducts. The calculated polychromatic quantum efficiencies (phi) of AZX at pH 4.5, 7 and 9 were 5.42 x 10(-3), 3.47 x 10(-3) and 3.06 x 10(-3) (degraded molecules per absorbed photon), respectively. The relatively narrow range of values indicates the stability of AZX with respect to photodegradation in the studied pH range. Results from the HPLC/MS analysis suggest that the phototransformation of AZX proceeds via multiple, parallel reaction pathways including: (1) photo-isomerization (E-->Z), (2) photo-hydrolysis of the methyl ester and of the nitrile group, (3) cleavage of the acrylate double bond, (4) photohydrolytic ether cleavage between the aromatic ring giving phenol, and (5) oxidative cleavage of the acrylate double bond.     

Concentrations of volatile organic compounds in an industrial area of Korea

We measured and analyzed daily mean concentrations of volatile organic compounds (VOC) at Ulsan industrial and downtown sites from 3 to 8 June 1997. The industrial site is situated at the boundary of a petrochemical complex and the other is at downtown area in Ulsan. At each site, we collected ambient air samples in passivated stainless-steel containers by using constant flow samplers and analyzed them by a GC-FID. At Ulsan industrial site, the concentrations and their daily variations of total VOC were higher than those at the downtown site. The concentrations of oxygenated hydrocarbons were the highest among seven hydrocarbon groups at both sites. The fraction of C₂–C₅ light hydrocarbon concentrations to C₂–C₉ hydrocarbons at Ulsan industrial site was higher than that in other industrial areas. It suggests that fugitive emissions of light hydrocarbons in Ulsan industrial areas might be higher than those of other industrial areas. Under favorable wind conditions, the influence of industrial emissions of VOC on the downtown hydrocarbon levels was observed.     

Plant–bacteria partnerships for the remediation of hydrocarbon contaminated soils

Plant–bacteria partnerships have been extensively studied and applied to improve crop yield. In addition to their application in agriculture, a promising field to exploit plant–bacteria partnerships is the remediation of soil and water polluted with hydrocarbons. Application of effective plant–bacteria partnerships for the remediation of hydrocarbons depend mainly on the presence and metabolic activities of plant associated rhizo- and endophytic bacteria possessing specific genes required for the degradation of hydrocarbon pollutants. Plants and their associated bacteria interact with each other whereby plant supplies the bacteria with a special carbon source that stimulates the bacteria to degrade organic contaminants in the soil. In return, plant associated-bacteria can support their host plant to overcome contaminated-induced stress responses, and improve plant growth and development. In addition, plants further get benefits from their associated-bacteria possessing hydrocarbon-degradation potential, leading to enhanced hydrocarbon mineralization and lowering of both phytotoxicity and evapotranspiration of volatile hydrocarbons. A better understanding of plant–bacteria partnerships could be exploited to enhance the remediation of hydrocarbon contaminated soils in conjunction with sustainable production of non-food crops for biomass and biofuel production.     

Adsorptive separation of cadmium from aqueous solutions and wastewaters by riverbed sand

Application of riverbed sand for the adsorptive separation of cadmium(II) from aqueous solutions has been investigated. Removal increased from 26.8 to 56.4% by decreasing the initial concentration of cadmium from 7.5 x 10(-5) to 1.0 x 10(-5)M at pH 6.5, 25 degrees C temperature, agitation speed of 100 rpm, 100 microm particle size and 1.0 x 10(-2) NaClO4 ionic strength. Process of separation is governed by first order rate kinetics. The value of rate constant of adsorption, k(ad), was found to be 2.30 x 10(-2)per min at 25 degrees C. Values of coefficient of mass transfer, beta L, were calculated and its value at 25 degrees C was found to be 1.92 x 10(-2)cm/s. Values of Langmuir constant were calculated. Values of thermodynamic parameters delta G0, delta H0 and delta S0 were also calculated and were recorded as -0.81 kcal/mol, -9.31 kcal/mol and -28.10 cal/mol at 25 degrees C. pH has been found to affect the removal of cadmium significantly and maximum removal, 58.4%, has been found at pH 8.5. Process can be used for treatment of cadmium(II) rich wastewaters.     

Solubilization properties of polycyclic aromatic hydrocarbons by saponin, a plant-derived biosurfactant

The enhanced solubilization of polycyclic aromatic hydrocarbons (PAHs) by saponin, a plant-derived non-ionic biosurfactant, was investigated. The results indicated that the solubilization capabilities of saponin for PAHs were greater than some representative synthetic non-ionic surfactants and showed strong dependence on solution pH and ionic strength. The molar solubilization ratio (MSR) of saponin for phenanthrene was about 3-6 times of those of the synthetic non-ionic surfactants, and decreased by about 70% with the increase of solution pH from 4.0 to 8.0, but increased by approximately 1 times with NaCl concentration increased from 0.01 to 1.0 M. Heavy metal ions can enhance saponin solubilization for phenanthrene and the corresponding MSR values increased by about 25% with the presence of 0.01 M of Cd²⁺ or Zn²⁺. Saponin is more effective in enhancing PAHs solubilization than synthetic non-ionic surfactants and has potential application in removing organic pollutants from contaminated soils.     

Micronucleus distribution in human peripheral blood lymphocytes treated in vitro with cadmium chloride in G0 and S phase of the cell cycle

Cadmium chloride (CdCl2 x H2O) in concentrations 10(-3) - 10(-6) M was tested for genotoxicity in human lymphocytes in vitro. The DNA damage was expressed through the occurrence of micronuclei (MN) and was detected using the cytochalasin-B-blocked MN assay. Human blood was treated in the G0 and S phase of the cell cycle. All except the highest concentration of cadmium chloride of 10(-3) M applied in the G0 phase of the cell cycle resulted in the increase in MN cells, but it was not statistically significant. Cadmium chloride added to the cultures in the concentration of 10(-3) M affected the cell growth regardless of the phase. Cadmium chloride added to cultures 24 h after their initiation (early S phase) was found to significantly increase the MN frequency in 10(-4) - 10(-6) M concentrations (P > 0.05).     

Chlorination of bisphenol A: kinetics and by-products formation

The kinetics of initial chlorination of bisphenol A (BPA) was studied between pH 2 and 11 at room temperature (20 +/- 2 degrees C). pH Profile of the apparent second-order rate constant of the reaction of BPA with chlorine were modeled considering the elementary reactions of HOCl with BPA species and an acid-catalyzed reaction. The predominant reactions at near neutral pH were the reactions of HOCl with the two phenolate species of BPA (k = 3.10 x 10(4) M(-1)s(-1) for BPA- and 6.62 x 10(4) M(-1) s(-1) for BPA(2-)). At near neutral pH, half-life times of BPA were calculated to be less than 1.5 h for chlorine residual higher than 0.2 mg l(-1). Chlorination of synthetic treated waters spiked with BPA showed that BPA disappeared within 4 h and that chlorinated bisphenol A congeners were rapidly formed and remained in solution for up to 10-20 h when low chlorine dosages are applied (0.5-1 mg l(-1)). To limit their presence in drinking water networks, it is then necessary to maintain high chlorine residuals that rapidly produce and decompose chlorinated bisphenol A congeners.     

Effect of biochar on the fate of volatile petroleum hydrocarbons in an aerobic sandy soil

Biochar addition to soil is currently being investigated as a novel technology to remediate polluted sites. A critical consideration is the impact of biochar on the intrinsic microbial pollutant degradation, in particular at sites polluted with a mixture of readily biodegradable and more persistent organic pollutants. We therefore studied the impact of biochar (2% on dry weight basis) on the fate of volatile petroleum hydrocarbons in an aerobic sandy soil with batch and column studies. The soil-water partitioning coefficient, K(d), was enhanced in the biochar-amended soil up to a factor 36, and petroleum hydrocarbon vapor migration was retarded accordingly. Despite increased sorption, in particular of monoaromatic hydrocarbons, the overall microbial respiration was comparable in the biochar-amended and unamended soil. This was due to more rapid biodegradation of linear, cyclic and branched alkanes in the biochar amended soil. We concluded that the total petroleum hydrocarbon degradation rate was controlled by a factor other than substrate availability and the reduced availability of monoaromatic hydrocarbons in the biochar amended soil led to greater biodegradation of the other petroleum compounds.