Electron-beam treatment of aromatic hydrocarbons that can be air-stripped from contaminated groundwater. 1. Model studies in aqueous solution

As a model for the electron-beam degradation of volatile aromatics (benzene, toluene, ethylbenzene, xylenes, BTEX) in groundwater strip gas, to be reported in Part 2, the gamma-radiolysis of benzene has been studied in aqueous solutions. Addition of *OH to the aromatic ring gives rise to hydroxycyclohexadienyl radicals which either dimerize or disproportionate. The various dimers undergo acid-catalyzed water elimination yielding biphenyl. Phenol is formed upon disproportionation directly, but also via dihydroxycyclohexadiene which subsequently undergoes acid-catalyzed water elimination. Co-radiolysis of benzene with nitrite generates *NO2 in addition to the hydroxycyclohexadienyl radical. These not only interact with one another (product: nitrobenzene via nitro-hydroxycyclohexadienes) but the *NO2 radical is also capable of abstracting cyclohexadienylic hydrogens. This reaction leads to the formation of 2- and 4-nitrophenol and to further nitrated products that were not identified. These are suggested to be formed in an analogous reaction of *NO2 with the hydroxycylohexadienyl dimers. The effect of O2 on these reactions and the relevance for the gas-phase radiolysis of BTEX is discussed.     

Radiation chemistry of methyl tert-butyl ether in aqueous solution

The chemical kinetics of the free-radical-induced degradation of the gasoline oxygenate methyl tert-butyl ether (MTBE) in water have been investigated. Rate constants for the reaction of MTBE with the hydroxyl radical, hydrated electron, and hydrogen atom were determined in aqueous solution at room temperature, using electron pulse radiolysis and absorption spectroscopy (*OH and e- aq) and EPR free induction decay attenuation (*H) measurements. The rate constant for hydroxyl radical reaction of (1.71 +/- 0.02) x 10(9) M(-1) s(-1) showed that the oxidative process was the dominant pathway, relative to MTBE reaction with hydrogen atoms, (3.49 +/- 0.06) x 10(6) M(-1) s(-1), or hydrated electrons, <8.0 x 10(6) M(-1) s(-1). The hydroxyl radical reaction gives a transient carbon-centered radical which subsequently reacts with dissolved oxygen to form peroxyl radicals, the rate constant for this reaction was (2.17 +/- 0.06) x 10(9) M(-1) s(-1). The second-order decay of the MTBE peroxyl radical was 2k = (6.0 +/- 0.3) x 10(8) M(-1) s(-1). These rate constants, along with preliminary MTBE degradation product distribution measurements, were incorporated into a kinetic model that compared the predicted MTBE removal from water against experimental measurements performed under large-scale electron beam treatment conditions.     

Photolysis of ozone in aqueous solutions in the presence of tertiary butanol

The ozone decomposition quantum yield (phi) in millimolar and higher-concentration aqueous tertiary butanol solution is 0.64 +/- 0.05 (observed over a wavelength range from 250 to 280 nm) and rises toward lower tertiary butanol concentrations (phi approximately 1.5 at 10(-5) M at pH 2) on account of the onset of the well-known *OH-radical-induced chain reaction. The destruction of the organic is initiated by hydrogen-atom abstraction through OH radicals which are produced via the reaction of the photolytically generated O(1D) with the solvent water at a quantum yield of phi(*OH) of about 0.1. There is no decomposition of ozone in the dark on the time scale of the photolysis experiment. The efficiency of tertiary butanol destruction with respect to ozone consumption ([O3]0 = 3 x 10(-4) M), defined by the ratio delta[t-BuOH]/delta[O3], termed eta(t-BuOH), is 0.26 at millimolar tertiary butanol concentrations, determined at the stage of essentially complete ozone consumption. It diminishes toward lower tertiary butanol concentrations (delta[t-BuOH]/delta[O3] approximately 0.17 at [t-BuOH]0 = 1 x 10(-4) M). Part of the effect of the ozone, apart from being a source of *OH radicals, rests on the intervention of HO2*/O2*- which is produced in the course of the peroxyl-radical chemistry of the tertiary butanol in this dioxygen-saturated environment and converted into further *OH radical by reaction with ozone. Moreover in this system, organic free radicals and peroxyl radicals react with the ozone. On the basis of the experimental and mechanistic-simulation data, the quantum yield of direct (by hv) ozone cleavage in aqueous solution is estimated at about 0.5.     

Hydroxyl radical generation mechanism during the redox cycling process of 1,4-naphthoquinone

Airborne quinones contribute to adverse health effects of ambient particles probably because of their ability to generate hydroxyl radicals (·OH) via redox cycling, but the mechanisms remain unclear. We examined the chemical mechanisms through which 1,4-naphthoquinone (1,4-NQ) induced ·OH, and the redox interactions between 1,4-NQ and ascorbate acid (AscH(2)). First, ·OH formation by 1,4-NQ was observed in cellular and acellular systems, and was enhanced by AscH(2). AscH(2) also exacerbated the cytotoxicity of 1,4-NQ in Ana-1 macrophages, at least partially due to enhanced ·OH generation. The detailed mechanism was studied in an AscH(2)/H(2)O(2) physiological system. The existence of a cyclic 1,4-NQ process was shown by detecting the corresponding semiquinone radical (NSQ·-) and hydroquinone (NQH(2)). 1,4-NQ was reduced primarily to NSQ·- by O2·- (which was from AscH(2) reacting with H(2)O(2)), not by AscH(2) as normally thought. At lower doses, 1,4-NQ consumed O2·- to suppress ·OH; however, at higher doses, 1,4-NQ presented a positive association with ·OH. The reaction of NSQ·- with H(2)O(2) to release ·OH was another important channel for OH radical formation except for Haber-Weiss reaction. As a reaction precursor for O2·-, the enhanced ·OH response to 1,4-NQ by AscH(2) was indirect. Reducing substrates were necessary to sustain the redox cycling of 1,4-NQ, leading to more ·OH and a deleterious end point.     

Electron pulse radiolysis determination of hydroxyl radical rate constants with Suwannee River fulvic acid and other dissolved organic matter isolates

Pulse radiolysis experiments were conducted on dissolved organic matter (DOM) samples isolated as hydrophobic and hydrophilic acids and neutrals from different sources (i.e., stream, lake, wastewater treatment plant). Absolute bimolecular reaction rate constants for the reaction of hydroxyl radicals (*OH) with DOM (k*(OH), DOM) were determined. k*(OH, DOM) values are expressed as moles of carbon. Based on direct measurement of transient DOM radicals (DOM*) and competition kinetic techniques, both using pulse radiolysis, the k*(OH, DOM) value for a standard fulvic acid from the Suwannee River purchased from the International Humic Substances Society was (1.60 +/- 0.24) x 10(8) M(-1) s(-1). Both pulse radiolysis methods yielded comparable k*(OH, DOM) values. The k*(OH, DOM) values for the seven DOM isolates from different sources ranged from 1.39 x 10(8) M(-1) s(-1) to 4.53 x 10(8) M(-1) s(-1), and averaged 2.23 x 108 M(-1) s(-1) (equivalent to 1.9 x 10(4) (mgC/L)(-1) s(-1)). These values represent the first direct measurements of k*(OH, DOM,) and they compare well with literature values obtained via competition kinetic techniques during ozone or ultraviolet irradiation experiments. More polar, lower-molecular-weight DOM isolates from wastewater have higher k*(OH, DOM) values. In addition, the formation (microsecond time scale) and decay (millisecond time scale) of DOM* transients were observed for the first time. DOM* from hydrophobic acids exhibited broader absorbance spectra than transphilic acids, while wastewater DOM isolates had narrower DOM* spectra more skewed toward shorter wavelengths than did DOM* spectra for hydrophobic acids.     

Photolysis of aqueous H2O2: quantum yield and applications for polychromatic UV actinometry in photoreactors

Methanol is used to measure the yield of *OH radicals produced in the photolysis of H2O2 in aqueous solutions. The UV photolysis of H202 generates *OH radicals, which in the presence of methanol, oxygen, and phosphate buffer form formaldehyde, namely, phi(HCHO) = phi(*OH). The quantum yield of *OH has been redetermined in view of literature inconsistencies resulting in phi(*OH) = 1.11 +/- 0.07 in the excitation range of 205-280 nm. The constancy of phi(*OH) and the ease and sensitivity of the formaldehyde product analysis makes the H2O2/CH3OH system suitable for polychromatic UV actinometry. In addition, the relatively low cost of the main components and the possibility of destroying the methanol before disposal qualify the system for both monochromatic and polychromatic actinometry in a large volume of water. The H2O2/CH3OH system was applied in different commercial UV photoreactors.     

Degradation of ozone-refractory organic phosphates in wastewater by ozone and ozone/hydrogen peroxide (peroxone): the role of ozone consumption by dissolved organic matter

Ozonation is very effective in eliminating micropollutants that react fast with ozone (k > 10(3) M(-1) s(-1)), but there are also ozone-refractory (k < 10 M(-1) s(-1)) micropollutants such as X-ray contrast media, organic phosphates, and others. Yet, they are degraded upon ozonation to some extent, and this is due to (?)OH radicals generated in the reaction of ozone with organic matter in wastewater (DOM, determined as DOC). The elimination of tri-n-butyl phosphate (TnBP) and tris-2-chloroisopropyl phosphate (TCPP), added to wastewater in trace amounts, was studied as a function of the ozone dose and found to follow first-order kinetics. TnBP and TCPP concentrations are halved at ozone to DOC ratios of ～0.25 and ～1.0, respectively. The (?)OH rate constant of TCPP was estimated at (7 ± 2) × 10(8) M(-1) s(-1) by pulse radiolysis. Addition of 1 mg H(2)O(2)/L for increasing the (?)OH yield had very little effect. This is due to the low rate of reaction of H(2)O(2) with ozone at wastewater conditions (pH 8) that competes unfavorably with the reaction of ozone with wastewater DOC. Simulations based on the reported (No?the et al., ES&T 2009, 43, 5990-5995) (?)OH yield (13%) and (?)OH scavenger capacity of wastewater (3.2 × 10(4) (mgC/L)(-1) s(-1)) confirm the experimental data. Based on a typically applied molar ratio of ozone and H(2)O(2) of 2, the contribution of H(2)O(2) addition on the (?)OH yield is shown to become important only at high ozone doses.     

Anchored oxygen-donor coordination to iron for photodegradation of organic pollutants

A photocatalyst of oxygen-donor coordination to iron, complex of 5-sulfosalicylic acid (SSA) with ferric ion, supported on resin to cycle Fe3+/Fe2+ center under visible irradiation can effectively generate *OH radicals from H2O2, leading to degradation of organic pollutants in water. The higher turnover number was achieved by this catalyst for the degradation of model compound than those reported for the general N-donor ligands catalysts. The reversible "on/ off" switching of Fe3+/Fe2+ complexation with SSA, coupled with the phenol/phenoxyl radical conversion of the o-phenoxyl moiety of SSA, produces an ideal catalytic system that separates the Fenton reaction and the followed oxidations by *OH radicals (in water phase) from the regeneration of the catalytic species, Fe (SSA)2-, which occurs on the surface of resin. This system not only inhibits the undesired destruction of the ligands by *OH radicals, improving the stability of the catalyst, but also avoids the unnecessary decomposition of H2O2 into HO2* that occurs in the homogeneous Fenton system. Therefore, the system suggests an efficient utilization of H2O2 for degradation of organic pollutants.     

Decomposition of hydrogen peroxide and organic compounds in the presence of dissolved iron and ferrihydrite

This work examines the contribution of solution phase reactions, especially those involving a chain reaction mechanism, to the decomposition of hydrogen peroxide (H2O2) and organic compounds in the presence of dissolved iron and ferrihydrite. In solutions at pH 4, where Fe was introduced as dissolved Fe(III), both H2O2 and 14C-labeled formic acid decomposed at measurable rates that agreed reasonably well with those predicted by a kinetic model of the chain reaction mechanism, using published rate constants extrapolated to pH 4. The ratio of the formic acid and H2O2 decomposition rates, as well as the dramatic effect of tert-butyl alcohol on these rates, confirmed that a solution chain reaction mechanism involving *OH controlled the decomposition kinetics of both compounds. In the presence of ferrihydrite as the iron source, the ratio of the rate of formic acid decomposition to that of H2O2 decomposition was significantly lower than that observed in the presence of only dissolved Fe. Moreover, neither rate diminished drastically upon addition of tert-butyl alcohol, indicating that the solution phase chain reaction is not a dominant decomposition pathway of H2O2 and formic acid. Relative decomposition rates of formic acid and a second *OH probe, benzoic acid, were consistent with oxidation of these compounds by *OH. These observations can be reproduced by a kinetic model including (a) decomposition of H2O2 at the iron oxide surface, producing *OH with lower yield than the reaction sequence with dissolved Fe, and (b) low concentrations of dissolved Fe in the presence of ferrihydrite, preventing propagation of the solution phase chain reaction.     

Hydroxyl radical production via the photo-Fenton reaction in the presence of fulvic acid

The photo-Fenton reaction, the reaction of photoproduced Fe(II) with H2O2 to form the highly reactive hydroxyl radical (OH*), could be an important source of OH* in sunlit natural waters. To determine if the photo-Fenton reaction is significant in mildly acidic surface waters, we conducted experiments simulating conditions representative of natural freshwaters using solutions of standard fulvic acid and amorphous iron oxide at pH 6.0. A probe method measuring 14CO2 produced by the reaction of 14C-labeled formate with OH* was used to detect small OH* production rates without otherwise influencing the chemical reactions occurring in the experiments. Net H2O2 accumulation was simultaneously measured using an acridinium ester chemiluminescence method. Measured losses of H2O2 by reaction with Fe(II) in dark experiments produced approximately the expected quantities of OH*. The difference between H2O2 accumulation in the presence and absence of Fe(III) in fulvic acid solutions exposed to light was interpreted as the loss of H2O2 by reaction with photoproduced Fe(II), consistent with measured OH* production rates. The Fe ligand desferrioxamine mesylate eliminated both OH* production and H2O2 photoloss induced by Fe. Our results imply that when Fe is a major sink of H2O2, the photo-Fenton reaction is likely to be the most important source of OH*, leading to a significant sink of organic compounds in a wide variety of sunlit freshwaters.     

Highly efficient liquid-phase photooxidation of an azo dye methyl orange over novel nanostructured porous titanate-based fiber of self-supported radially aligned H2Ti8O17 x 1.5H2O nanorods

Novel nanostructured porous fibers of self-supported, radially aligned H2Ti8O17 x 1.5H2O nanorods were prepared from layered H2Ti4O9 x 1.2H2O tetratitanate fibers by novel solvothermal reaction in glycerine at 150-250 degrees C. The H2Ti8O17 x 1.5H2O fibers with diameters of 0.5-1.5 microm and lengths of 10-20 microm consist of multi-scale nanopores and nanostructures. They also are of high crystallinity, large surface area of 127 m2 g(-1), and stable phase up to 350 degrees C. Photocatalytic activity of the H2Ti8O17 x 1.5H2O fibers was evaluated in aqueous photooxidation of an azo dye methyl orange in the presence of UV irradiation and 02, using P-25 as the standard sample. Both the photocatalytic activity and the dispersity-agglomeration property of H2Ti8O17 x 1.5H2O fibers are pH-controllable. Highly photooxidative activity, superior to that of P-25, occurs at pH 6.0-11.0 due to certain distinguishable material characteristics and to large amounts of adsorbed reactants of surface active OH* free radicals, surface hydroxyl OH, O2*-, O*OH, and methyl orange. The agglomeration of H2Ti8O17 x 1.5H2O fibers becomes more serious from pH 2.0 to pH 5.0 and from pH 6.0 to pH 11.0. Well-dispersed H2Ti8O17 x 1.5H2O fibers occur at pH 6.0. Both the total photodegradation of waste chemicals and the entire sedimentation of H2Ti8O17 x 1.5H2O fibers can be timed to end simultaneously at suitable pH value. The photocatalyst-free reaction solution is then easily removed, and the fresh wastewater is added again. Standard unit operation processes of chemical engineering are used to design a continuous, low-cost, large-scale, liquid-phase photocatalysis technique based on the H2Ti8O17 x 1.5H2O fibers.     

猕猴桃根提取物体外抗氧化作用的研究

探讨猕猴桃根提取物的体外抗氧化作用.采用DPPH自由基、超氧阴离子、羟基自由基、过氧化氢和还原力的反应体系,测定猕猴桃根提取物的体外抗氧化作用,并用VC进行对照实验.实验条件下,ERHM对DPPH自由基、超氧阴离子(·O2-)、羟基自由基(·OH)、过氧化氢H2O2等均有较强的清除或抑制作用,且显示较好的量效关系,同时具有一定的还原力.其消除DPPH自由基的EC50为8.03 μg/mL,清除超氧阴离子(·O2-)的EC5o为1.28 mg/mL,抑制羟基自由基(·OH)能力可达69.4％,浓度为100 μg/mL时对过氧化氢(H2O2)的清除率为42％.猕猴桃根提取物具有较强的还原力,能有效清除DPPH和超氧阴离子自由基,并抑制羟基自由基的产生.所以,ERHM有效成分具有较为显著的抗氧化作用.     

Iron-catalyzed oxidation of arsenic(III) by oxygen and by hydrogen peroxide: pH-dependent formation of oxidants in the Fenton reaction

The oxidation kinetics of As(III) with natural and technical oxidants is still notwell understood, despite its importance in understanding the behavior of arsenic in the environment and in arsenic removal procedures. We have studied the oxidation of 6.6 microM As(II) by dissolved oxygen and hydrogen peroxide in the presence of Fe(II,III) at pH 3.5-7.5, on a time scale of hours. As(III) was not measurably oxidized by O2, 20-100 microM H2O2, dissolved Fe(III), or iron(III) (hydr)-oxides as single oxidants, respectively. In contrast, As(III) was partially or completely oxidized in parallel to the oxidation of 20-90 microM Fe(II) by oxygen and by 20 microM H2O2 in aerated solutions. Addition of 2-propanol as an *OH-radical scavenger quenched the As(III) oxidation at low pH but had little effect at neutral pH. High bicarbonate concentrations (100 mM) lead to increased oxidation of As-(III). On the basis of these results, a reaction scheme is proposed in which H2O2 and Fe(II) form *OH radicals at low pH but a different oxidant, possibly an Fe(IV) species, at higher pH. With bicarbonate present, carbonate radicals might also be produced. The oxidant formed at neutral pH oxidizes As(III) and Fe(II) but does not react competitively with 2-propanol. Kinetic modeling of all data simultaneously explains the results quantitatively and provides estimates for reaction rate constants. The observation that As(III) is oxidized in parallel to the oxidation of Fe(II) by O2 and by H2O2 and that the As(III) oxidation is not inhibited by *OH-radical scavengers at neutral pH is significant for the understanding of arsenic redox reactions in the environment and in arsenic removal processes as well as for the understanding of Fenton reactions in general.     

Visible-light-assisted degradation of dye pollutants over Fe(III)-loaded resin in the presence of H2O2 at neutral pH values

A novel catalyst was synthesized by direct exchange of ferric ions onto a cationic resin (Amberlite IRA200). Upon visible light irradiation (lambda > 420 nm) in the presence of H2O2, this catalyst was found to be highly effective for the degradation of nonbiodegradable cationic dyes, Malachite green, Rhodamine B, and Methylene blue, even at neutral pH values. It was also easy to separate from the degraded solution. By total organic carbon, FT-IR, and GC-MS analysis, the degradation process of Malachite green was shown to proceed with demethylation and phenyl ring openings into CO2 and small molecular compounds. EPR studies revealed that *OH radicals, other than *OOH/O2*-, were involved as the active species. A possible reaction mechanism is proposed on the basis of all the information obtained under various experimental conditions.     

采后钙处理对“安哥诺”李果实的贮藏效果及抗氧化能力的影响

探讨不同采后钙处理对“安哥诺”李果实的贮藏效果以及抗氧化能力的影响。结果表明：氯化钙和丙酸钙均能有效降低李果实的发病率,其中氯化钙的作用效果更显著,但对果皮与果肉色泽没有显著影响;乳酸钙则加速李果实的病害发生,降低李果皮a* 值、果肉L* 值与b* 值,提高果肉a* 值;三种钙处理均诱导了采后李果实过氧化氢含量的积累,加剧了总抗氧化能力、超氧阴离子自由基清除能力、DPPH 自由基清除能力的下降,提高了羟自由基清除能力,但李果实的腐烂率与过氧化氢含量和总抗氧化能力之间不存在显著相关性。李果实总抗氧化能力、超氧阴离子自由基以及DPPH 自由基清除能力与总酚、总黄酮含量呈极显著正相关。     

Kinetics and mechanism of photoactivated periodate reaction with 4-chlorophenol in acidic solution

The application of photoactivated periodate (UV/IO4-) to the degradation of 4-chlorophenol (4-CP) was explored in this study. Under low irradiation intensities (23 microW/cm2), wavelength of 266 nm, and pH 3, 4-CP was observed to degrade by pseudo-first-order reaction kinetics. The small reduction in 4-CP degradation in the presence of tert-butyl alcohol (t-BuOH) suggests that degradation of 4-CP by UV/IO4- was not dominated by an OH* pathway. O3 production was suppressed in the presence of t-BuOH under O2-limited environments and in the presence of 4-CP. Faster degradation of 4-CP in the presence of an OH* scavenger under nitrogen purging as compared to air-saturated conditions indicates that O(3P) is an important reactive species with 4-CP in this system. When 4-CP is added to the system, IO3- production is enhanced. On the basis of the elimination of potential reaction pathways, O(3P) and IO3* are suspected reactive species with 4-CP in this system.     

2-Formylcinnamaldehyde Formation Yield from the OH Radical-Initiated Reaction of Naphthalene: Effect of NO(2) Concentration

Naphthalene, typically the most abundant polycyclic aromatic hydrocarbon in the atmosphere, reacts with OH radicals by addition to form OH-naphthalene adducts. These OH-naphthalene adducts react with O(2) and NO(2), with the two reactions being of equal importance in air at an NO(2) mixing ratio of ～60 ppbv. 2-Formylcinnamaldehyde [o-HC(O)C(6)H(4)CH═CHCHO] is a major product of the OH radical-initiated reaction of naphthalene, with a yield from the reaction of OH-naphthalene adducts with NO(2) of ～56%. We have measured, on a relative basis, the formation yield of 2-formylcinnamaldehyde from the OH radical-initiated reaction of naphthalene in air at average NO(2) concentrations of 1.2 × 10(11), 1.44 × 10(12), and 1.44 × 10(13) molecules cm(-3) (mixing ratios of 0.005, 0.06, and 0.6 ppmv, respectively). These NO(2) concentrations cover the range of conditions corresponding to the OH-naphthalene adducts reacting ～90% of the time with O(2) to ～90% of the time with NO(2). The 2-formylcinnamaldehyde formation yield decreased with decreasing NO(2) concentration, and a yield from the OH-naphthalene adducts + O(2) reaction of 14% is obtained based on a 56% yield from the OH-naphthalene adducts + NO(2) reaction. Based on previous measurements of glyoxal and phthaldialdehyde from the naphthalene + OH reaction and literature data for the OH radical-initiated reactions of monocyclic aromatic hydrocarbons, the reactions of OH-naphthalene adducts with O(2) appear to differ significantly from the OH-monocyclic adduct + O(2) reactions.     

Electron-beam treatment of aromatic hydrocarbons that can be air-stripped from contaminated groundwater. 2. Gas-phase studies

The electron-beam (EB) degradation of volatile aromatics (benzene, toluene, ethylbenzene, xylenes: BTEX) in groundwater strip gas, which in the present work has been modeled by the introduction of the desired aromatic(s) to a stream of air or another gas, such as oxygen, is initiated essentially by the addition of *OH radicals to the aromatic ring, giving rise to hydroxycyclohexadienyl radicals, which form the corresponding peroxyl radicals upon addition of oxygen. As studied in some detail with benzene as a BTEX representative, various reactions of these lead to numerous oxidation products in a cascade of reactions, including the decomposition of products under the prevailing conditions of high turnover of the initial aromatic. Importantly, hydroxycyclohexadienylperoxyl radical formation is partly reversible, and the reactions of the hydroxycyclohexadienyl radicals, which thus have a significant presence in these systems, must therefore also be taken into consideration. In the gas phase, in contrast to the aqueous phase (see Part 1), the reactions of the hydroxycyclohexadienyl radicals lead to oligomeric products that appear to contribute, in addition to ionic clusters, to nucleation for the aerosols observed. Various nitrated products, among them nitrophenols, are observed when air is used for the stripping. However, these studies did not clear the pilot plant stage, since BTEX degradation using a bioreactor carried out in parallel was so successful that the EB technology was judged to be noncompetitive. As for the latter, expensive equipment consisting of a stripper, the EB machine, and an aerosol precipitator would be required. The condensed aerosols are biorefractory and would require further treatment for detoxification.