Formation of cyanide ion or cyanogen chloride through the cleavage of aromatic rings by nitrous acid or chlorine. VIII. On the reaction of humic acid with hypochlorous acid in the presence of ammonium ion

Cyanogen chloride was formed by the reaction of humic acid with hypochlorous acid in the presence of ammonium ion. Furthermore, cyanogen chloride was also formed when ammonium ion and hypochlorous acid were added to raw water sampled at water treatment plants.     

Formation of cyanide ion or cyanogen chloride through the cleavage of aromatic rings by nitrous acid or chlorine. XI On the reaction of purine bases with hypochlorous acid in the presence of ammonium ion

Cyanogen chloride was formed by the reactions of purine bases(adenine and guanine) with hypochlorous acid in the presence of ammonium ion. The origin of the carbon and nitrogen atoms of cyanogen chloride formed from adenine was investigated by use of synthetic adenines variously labeled with the isotope of nitrogen(¹⁵N) or carbon(¹³C).     

Formation of cyanide ion or cyanogen chloride through the cleavage of aromatic rings by nitrous acid or chlorine. IX. On the reactions of chlorinated, nitrated, carboxylated or methylated benzene derivatives with hypochlorous acid in the presence of ammonium ion

Chlorinated, nitrated, carboxylated or methylated benzenes, phenols and anilines reacted with chloramine to give cyanogen chloride, independently of the positions and the numbers of the substituents. Among these compounds, 2,4,6-trichlorophenol afforded cyanogen chloride in a relatively high yield of 13.3%, and the intermediates in the reaction were 2,6-dichloro-1,4-benzoquinone-4-(N-chloro)imine and 4,6-dichloro-1,2-benzoquinone-2-(N-chloro)-imine, of which the latter was the main intermediate.     

Chloroperoxidase-mediated chlorination of aromatic groups in fulvic acid

The aim of the present study is to investigate whether exo-enzymatically mediated chlorination of fulvic acid (FA) results in the formation of chlorinated groups within the macromolecules which correspond to those which were previously detected in soil and surface water samples. The chlorination was carried out by exposing FA to a commercial chloroperoxidase (CPO) in the presence of chloride and hydrogen peroxide. The exposed FA was then chemically degraded using an oxidative technique and finally analysed for four different aromatic groups and their chlorinated analogues. The particular aromatic groups included were the methyl esters of 4-ethoxybenzoic acid, 3-methoxy-4-ethoxybenzoic acid, 3,4-diethoxybenzoic acid, and 3,5-dimethoxy-4-ethoxybenzoic acid, along with their mono- and dichlorinated analogues. Prior to the chemical degradation procedure, the FA was analysed for AOX (adsorbable organic halogens) and chlorinated acetic acids. The original FA contained 1.4 mg Cl(org) g(-1) and detectable amounts of two chlorinated aromatic groups. After exposure to the enzyme, the concentration of AOX increased to 44.3 mg Cl(org) g(-1) and detectable amounts of four chlorinated aromatic groups as well as di- and trichloroacetic acid were found.     

Humic acid complexation of basic and neutral polycyclic aromatic compounds

Complexation by humic acid (HA) of basic (quinoline) and neutral (naphthalene) polycyclic aromatic compounds (PACs) was compared using fluorescence spectroscopy and equilibrium dialysis (ED). These compounds sorb to HA via cation exchange and hydrophobic interactions, respectively. Ionization of quinoline strongly affects its sorption to HA; maximum sorption is observed at pH close to logKb (4.92), and competition with H+ and electrolyte cation (Li+) is evident. Spectroscopic experiments indicate that quinolinium (QH+) cation fluorescence is quenched via a static mechanism (i.e., a dark complex is formed) when the protonated form is adsorbed via ion exchange to HA. The extent of sorption, calculated from fluorescence data using the Stern-Volmer equation, was compared to independent ED measurements. Although both methods indicated the same trends with solution chemistry, fluorescence quenching data suggested more extensive complexation than that measured using ED. In contrast to ionizable PACs, studied here and previously, interaction of naphthalene with HA is unaffected by changes in solution conditions (pH, ionic strength).     

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.     

Dissipation of polycyclic aromatic hydrocarbons from soil added with manure or vermicompost

The dissipation of three PAHs, i.e., 500 mg phenanthrene kg(-1) soil, 350 mg anthracene kg(-1) soil and 150 mg benzo(a)pyrene kg(-1) soil, was investigated in soil from Acolman (México) added with cow manure or vermicompost while production of CO(2) and inorganic N was monitored. At day 0, recovery of added phenanthrene was 95%, anthracene 96% and benzo(a)pyrene 100% in sterilized soil and concentrations did not change significantly in sterilized soil over time. Application of organic material did not affect the concentration of phenanthrene and anthracene, which decreased sharply in the unsterilized soil in the first weeks of the incubation. Less than 3% of the added phenanthrene was detected after 100 days and less than 8.5% of the added anthracene (mean of the two experiments). The decrease in concentration of benzo(a)pyrene (BaP) was not fast as that of phenathrene and anthracene, and 22% was extractable from soil still after 100days. It was concluded that addition of farm yard manure (FYM) and vermicompost only had an effect on the initial dissipation of phenanthrene, anthracene and benzo(a)pyrene in soil of Acolman.     

Generation of cyanide ion by the reaction of phenol with nitrous acid in wastewater

It was found that phenol reacts with nitrous acid to produce cyanide ions. Cyanide ion generation is attributed to the conversion of phenol to nitrosophenol through the well-known nitrosation reaction, and decomposition of benzoquinonoxim to form cyanide and aliphatic compound.     

水环境中腐殖酸与镉离子结合作用的影响因素

通过测定不同化学条件下腐殖酸与镉离子作用后的游离态镉离子浓度及其结合率,研究各因素对腐殖酸与镉离子作用的影响。研究结果表明,pH值、离子强度、投加镉离子总浓度、腐殖酸浓度和反应温度均影响腐殖酸与镉离子的结合。pH值在4.5~6.5范围内,随pH值升高,腐殖酸与Cd²⁺的结合率增大,游离态Cd²⁺浓度减少。溶液的离子强度增大对结合反应有抑制作用。投加Cd²⁺总浓度的增大会导致结合态Cd²⁺浓度和游离态Cd²⁺浓度逐渐增加,而其结合率逐渐减小。腐殖酸浓度逐渐增大,使Cd²⁺和腐殖酸的结合率逐渐增大。在20℃~50℃范围内时,随反应温度升高,游离态Cd²⁺浓度逐渐减小,其结合率逐渐增加。     

Selected ion chromatograms and tandem mass spectrometry for detection of trace polycyclic aromatic hydrocarbons in diesel exhaust

Polycyclic aromatic hydrocarbon (PAH) measurements are essential for scientists and engineers who investigate these anthropogenic compounds. Diesel engines contribute to the problem, so analysts are measuring PAHs from these sources. However, diesel exhaust presents special problems for precise analytical measurements. The exhaust matrix is very complex; consequently, PAH detection sensitivity deteriorates, especially for trace PAHs in the exhaust. Yet, these are conditions and amounts that exist in real samples. Nonetheless, selected ion chromatogram (SIC) and tandem mass spectrometry (MS/MS) techniques improve trace PAH detection; ion trap technology makes both mass techniques possible. The purpose of this investigation was to evaluate SIC and MS/MS for applications to measure PAHs in diesel exhaust samples. The signal-to-noise ratio for accurate quantitation improves, relative to traditional mass techniques, because these techniques ignore or eliminate interfering components. On a VF-5MS chromatographic column, these techniques improve sensitivity and reproducibility. They produce a superior limit of detection in the useful range for PAH samples extracted from actual engine exhaust, 10-30 pg for the smaller PAHs and 1-6 ng for the larger PAHs. The results with SIC and MS/MS are reproducible, so analysts can report PAH amounts with defined statistical confidence intervals. SIC and MS/MS improve detection for trace PAHs in convoluted diesel exhaust samples.     

Intercomparison of the measurements of oxalic acid in aerosols by gas chromatography and ion chromatography

Oxalate, the anion of oxalic acid, is one of the most abundant measurable organic species in atmospheric aerosols. Traditionally, this bifunctional species has been measured by gas chromatography (GC) after derivatization to butyl ester and by ion chromatography (IC) without derivatization. However, there are few published comparisons of the two techniques. Here, we report the results of an intercomparison study for the measurement of oxalic acid in Arctic aerosols (<2.5 μm, n = 82) collected in 1992 using GC and IC. The concentrations of oxalic acid by GC ranged from 6.5–59.1 ng m^?3 (av. 26.0 ng m^?3, median 26.2 ng m^?3) whereas those by IC ranged from 6.6–52.1 ng m^?3 (av. 26.6 ng m^?3, median 25.4 ng m^?3). They showed a good correlation (r = 0.84) with a slope of 0.96. Thus, observations of oxalate obtained by GC employing dibutyl esters are almost equal to those by IC. Because the accuracy of oxalic acid by GC method largely depends on the method used, it is important to strictly examine the recovery in each study.     

High chrome exhaustion in a non-float tanning process using a sulphonic aromatic acid

Tanning processes performed in drums consume large amounts of water and chemicals, most of which end up in the wastewater. This study explores an alternative approach at an industrial scale to the traditional pickle-chrome tanning method. The new method replaces formic and sulphuric acids with sulphonic aromatic acid. Because it is done without float, there is a sizeable reduction in the amount of added salt and chrome salt as well as an increase in temperatures at the end of the tanning process. From an environmental perspective, the new method offers important advantages. For instance, there is no float addition in the tannage. Also, there are reductions of 94% and 99%, respectively, in the discharge of chlorides and chrome, as well as a 75% reduction in the residual float. Our financial assessment demonstrated that the new method is 42% cheaper than a traditional approach.     

交联腐殖酸CHA对水体中铅的吸附性能

通过环氧氯丙烷交联及多胺改性的方法,制备得到新型交联腐殖酸CHA。利用FTIR对其结构进行了表征,并重点考察了吸附温度等不同因素对CHA吸附水体中铅离子性能的影响。结果表明,交联腐殖酸CHA对水体中铅离子具有优异的吸附性能,平衡吸附容量可达到219.3 mg/g,远高于常规高温焙烧方法制得腐殖酸的吸附性能。CHA的吸附性能随反应温度、溶液pH的升高而增大,其吸附过程符合Langmuir吸附方程。     

Negative ion chemical ionization mass spectrometry - a useful technique for the selective detection of polar substituted polycyclic aromatic hydrocarbons with mutagenic properties

Earlier studies have shown that many compounds with toxic properties are able to form stable negative ions. The negative ion mass spectrometric response of polar substances found in indoor air extracts from aluminium smelters was determined and compared with available mutagenicity data. The results indicate that the relationship mentioned above also is valid for polar compounds.     

Coagulation characteristics of humic acid modified with glucosamine or taurine

To suppress the coagulation of humic acid (HA) in aqueous solutions, HA was modified with hydrophilic amines, such as glucosamine or taurine. These amines were attached to carboxyl groups in HA via amide bond formation. The degree of modification (R(m)) was estimated to be 21-38%. Infrared spectra of the modified HAs were also consistent with the presence of amide bonds. Acid-base titration showed that the average acid-dissociation constant (pK(app)) of the HA samples was increased by the modification. The Ca(2+) binding capacity of HA decreased with an increase in R(m) value. Critical pH or Ca(2+) concentration, at which HA coagulation occurs, was increased as the result of the modification. These critical points for taurine-HA were higher than those for glucosamine-HA. This is mainly due to electrostatic repulsion by sulfonate groups in taurine. These results indicate that the coagulation of HA is suppressed by modifying the molecules with glucosamine or taurine.     

腐植酸对多环芳烃在污染土壤中淋出及截留分解的效果研究

多环芳烃是固废拆解地一类污染较严重的有毒有机物质,用腐植酸作表面活性剂淋洗污染土壤起到较好的增溶及截留分解污染物的作用,达到修复污染土壤的目的。实验结果表明,随着腐植酸加入量的增加,菲、萘、荧蒽、芘和∑PAHs的淋出量显著提高,在污染红壤中最大淋出率分别为52.9%、70.1%、30.5%、46.1%和42.8%,在污染水稻土中最大淋出率分别为51.8%、67.3%、35.0%、38.3%和35.5%,同时多环芳烃的截留分解率也相对较高,而污染红壤和水稻土的总修复率分别达到56.3%和49.8%。