Sulphur-containing metabolites of the fungicides pentachloronitrobenzene (PCNB) and hexachlorobenzene (HCB) I. Syntheses

Syntheses of sulphur-containing metabolites of the fungicides pentachloronitrobenzene and hexachlorobenzene are described.     

Synthesis of polychlorinated biphenyls (PCBs) using the Suzuki-coupling

An improved synthesis of polychlorinated biphenyls (PCBs) utilizing a palladium-catalyzed cross-coupling reaction (Suzuki-coupling) is described. The coupling of (chlorinated) aryl boronic acids 1-3 with bromochlorobenzenes 4 using the standard conditions of the Suzuki-coupling gave the desired PCB congeners 5-7 in good to excellent yields. The self-coupling product of the aryl boronic acids is the major impurity of this reaction. 3,4,5-trichlorophenyl derivatives such as 10 can be synthesized by coupling of an aryl boronic acid with the corresponding bromochloroaniline 8. The approach offers the advantage of high selectivity and good yields compared to conventional methods such as the Cadogan reaction and allows the use of less toxic starting materials.     

Metabolism of 3-hydroxybenzo (a) pyrene in rat,isolated hepatocytes and kidney

After intravenous injection of 3-hydroxybenzo (a) pyrene into rat, benzo (a) pyrene-diols were detected in urine, and $\text{in vitro}$ experiment using isolated hepatocytes and sliced kidney also indicated the metabolism of 3-hydroxybenzo (a) pyrene to diol derivatives. THese results suggested the presence of unknown metabolic pathway of benzo (a) pyrene-phenols such as 3-hydroxybenzo (a) pyrene to diol derivatives both $\text{in vivo}$ and $\text{in vitro}$.     

Effects of heterocyclic PAHs (N, S, O) on the biodegradation of typical tar oil PAHs in a soil/compost mixture

The interaction phenomena during the biodegradation of typical coal tar polycyclic aromatic hydrocarbons and their heterocyclic analogues (N, S, O) were investigated in an artificially contaminated AhA1-horizon/compost mixture. All compounds were partly or completely biodegraded. Degradation of two- to five-ring PAHs was inhibited by the presence of hetero-PAHs, whereas degradation of just some hetero-PAHs was inhibited by the presence of PAHs. Among the hetero-PAHs the sulphur-containing compounds were less susceptible to degradation than the corresponding oxygen- or nitrogen-containing analogues. The basic azaarene acridine showed an extreme persistence and strong sorption to the soil matrix proved by an increase of recovery after saponification of the soil matrix.     

Removal of As(III) and As(V) from water by chitosan and chitosan derivatives: a review

As arsenic removal becomes a global concern, the development of removal processes for arsenic treatment is still a major challenge. With regard to environmental compatibility and cheapness, chitosan and chitosan derivatives are considered as a promising removal technology for arsenic. Chitosan and chitosan derivatives possess the properties of low cost and good sorption on the arsenic removal. The present review is concerned about the present understanding of the mechanisms involved in sorption processes. Further on, detailed discussions are given of the effects of various factors on the performance of chitosan and chitosan derivatives in arsenic treatment processes. Finally, special attention is paid to the future challenges of chitosan and chitosan derivatives utilized for industrial arsenic treatment.     

N-Nitroso compounds produced in deer mouse (Peromyscus maniculatus) GI tracts following hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) exposure

Given the potent carcinogenic effects of most N-nitroso compounds, the reductive transformation of the common explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) to a group of N-nitroso derivatives, hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX), hexahydro-1,3-dinitroso-5-nitro-1,3,5-triazine (DNX), and hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX) in the environment have caused concerns among the general public. Questions are arising about whether the same transformations also occur in mammals, and if true, to what extent. This study investigated the N-nitroso derivatives production in the deer mouse GI tract following RDX administration. Findings verified that such transformations do occur in the mammalian GI tract at notable levels: the average MNX concentrations in deer mice stomach were 85 microg/kg and 1318 microg/kg for exposure to 10mg/kg and 100mg/kg diet, respectively. DNX in stomach were 217 microg/kg for the 10mg/kg dose group and 498 microg/kg for the 100mg/kg dose group. Changes in other toxic endpoints including body weight gain, food consumption, organ weight, and behavior were also reported.     

Monitoring of bisphenol A diglycidyl ether (BADGE) and some derivatives in fish products in the Turkey market

The exposure to bisphenols and their derivatives was assessed in 33 fish products sold in Turkey using high-performance liquid chromatography-tandem mass spectrometry (LC–MS/MS). BADGE was determined in only four samples at concentrations ranging between 0.06 and 0.22 mg/kg. As the most abundant bisphenol groups, BADGE-hydrolyzed products such as BADGE·H₂O and BADGE·2H₂O were present in nine and fourteen samples in the range between 0.06–0.16 and 0.06–0.72 mg/kg, respectively. The total concentration of BADGE and hydrolyzed products was below the specific migration limit (SML) value of 9 mg/kg food, which in the European Union stated as tolerable. Chlorinated derivatives of BADGE were detected in fewer samples compared with hydrolyzed ones. BADGE·H₂O·HCl was the predominant migrant among chlorinated derivatives and was present in seven samples in a range between 0.02 and 0.06 mg/kg. All other samples contained less than or equal to 0.03 mg/kg of BADGE·HCl and BADGE·2HCl. The sum of these derivatives was lower than the SML value (1 mg/kg) of BADGE chlorohydrins legislated by the European Union. Besides these migrants, the analyzed samples did not contain any BFDGE and 3R-NOGE, which are prohibited in manufacturing food contact materials.

     

Degradation of ciprofloxacin by cryptomelane-type manganese(III/IV) oxides

The objective of this study is to investigate and understand the oxidizing properties of a manganese oxide, specifically synthetic cryptomelane (KMn₈O₁₆) and its derivatives, in aqueous solution. Ciprofloxacin (CIP), a commonly used fluoroquinolone antibiotic, was used as the probe. Synthetic cryptomelane, known as octahedral molecular sieves (OMS-2), was synthesized, and its derivatives were prepared by adding transition metal oxides, V₂O₅ or MoO₃, as dopants during synthesis. The solids were characterized by x-ray powder diffraction (XRD), SEM–energy-dispersive spectrometry (SEM-EDX), x-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectra (FTIR), Raman spectra, and N₂-Brunauer-Emmett-Teller method. Degradation of CIP by different doped OMS-2 was carried out. Process conditions were optimized using response surface methodology (RSM). XRD patterns indicated the crystal phase of regular and doped OMS-2 as the cryptomelane type. Presence of the dopants in doped cryptomelane was confirmed by SEM-EDX and XPS. FTIR and Raman results suggested that the dopants were substituted into the framework in place of manganese. SEM images, XRD analysis, and surface area analysis of doped OMS-2 indicated decreased particle size, decreased crystallinity, and increased surface area compared to regular OMS-2. Higher oxidizing reactivity of doped OMS-2 was also observed with increased CIP removal rates from aqueous solution. The enhancement of reactivity may be due to the increase of surface areas. Nine percent Mo/OMS-2, the most effective oxidant of all synthesized derivatives, was selected for optimization study. Favorable treatment conditions were obtained using RSM at pH 3 with molar ratio [9 % Mo/OMS-2]/[CIP]?≥?50. Under such conditions, more than 90 % CIP can be removed in 30 min. The degradation kinetics was modeled by a modified first order rate with introduction of a retardation factor-α (R ²?>?0.98). Analysis of degradation products indicated that oxidation takes place mainly on the piperazine ring of CIP.     

Theoretical studies of the conformations and 19F NMR spectra of linear and a branched perfluorooctanesulfonamide (PFOSAmide)

Technical perfluorooctanesulfonate (PFOS) and its derivatives, such as perfluorooctanesulfonamide (PFOSA), are not clean compounds but, instead, complex mixtures of linear and branched isomers, and other compounds including sulfonate homologues. Questions have been raised as to whether the linear and the branched isomers behave differently in the environment. However, little is known about the physical properties or the finer details of the structures of the individual branched isomers. This study sought an effective computational method to model the preferred conformations of PFOS derivatives, and the energy differences between them and to determine if these results can be used to explain the temperature dependence of their NMR spectra. Good predictions of the 19F chemical shifts were obtained for some PFOSA-type molecules with a computational approach [B3LYP-GIAO/6-31++G(d,p)//B3LYP/6-31G(d,p)] that is relatively inexpensive. Large 5JFF couplings found in one of the branched isomers could be rationalized on the basis of the relevant F-F distances in the optimized structure. At low temperatures, the splitting observed in the NMR spectrum at C-1 for these sulfonamides can be explained by the existence of the two conformers predicted by the computations.     

Microbial degradation of bis(tributyltin) oxide

The degradation of the biocide bis (tributyltin) oxide by pur cultures of microorganisms has been studied. Attempts to isolate microorganisms able to utilize bis (tributyltin) oxide as sole carbon source, were unsuccessful. Of many bacterial species investigated $\text{Pseudomonas aeruginosa}$ and $\text{Alcaligenes faecalis}$ degraded sublethal amounts of bis (tributyltin) oxide during aerobic growth in the presence of suitable carbon sources. $\text{P. aeruginosa}$ converted bis (tributyltin) oxide into monobutyltin and small amounts of dibutyltin derivatives. Similar results were obtained with growing mycelium of $\text{Coniophora puteana}$, $\text{Trametes versicolor}$ and $\text{Chaetomium globosum}$. Microbial conversion of monobutyltin trichloride was not observed. Dibutyltin dichloride was converted into monobutyltin derivatives under certain sterile conditions.     

Fe(III) promoted LAS (linear alkylbenzenesulfonate) removal from waters

The mechanisms of the interactions between Fe(III) aquacomplexes and surfactants were investigated; three alkylbenzenzsulfonates, two surfactants (octylbenzenesulfonate (OBS) and dodecylbenzenesulfonate (DBS)), and a shorter derivative (ethylbenzenesulfonate (EBS)) were studied. The results with OBS show evidence for three different ways in which Fe(III) interferes with the surfactant: the widely described flocculation process, complexation of Fe(OH)2+ (aquacomplexes) by the surfactant, and a redox reaction. The formation of a weak complex is maximum for a ratio of three between the monomeric aquacomplex [FeOH(H2O)5]2+ and OBS. In the presence of oxygen, an intramolecular redox reaction occurs inside the complex. The interaction between commercial DBS and Fe(III) was also investigated. Immediate precipitation occurred, mainly involving derivatives of higher molecular weights that are contained in the DBS samples. The constituents with the shortest alkyl chain were not affected by the presence of Fe(III) as it was also observed with EBS.     

Chemical and biochemical generation of carbohydrates from lignocellulose-feedstock (Lupinus nootkatensis)--quantification of glucose

Different chemical and enzymatic methods were applied for the hydrolysis of main stems from Lupinus nootkatensis (harvest November 2002). The whole process (all steps) is based on the lignocellulose-feedstock biorefinery regime. The acid hydrolysis of L. was performed with concentrated hydrochloric acid; advantages in this process are exothermic hydrolysis and the possibility of acid recovery. Enzymatic hydrolysis achieved high yields of fermentable carbohydrates (regarding to input cellulose) with high selectivity. However, this way requires the generation of cellulose from L. by chemical pulping. Monosaccharide derivatives thus obtained were identified by their GC retention times and the corresponding MS fragmentation. Hexamethyldisilazane was used as derivatization reagent to prepare the trimethylsilyl derivatives of the carbohydrates and of the degradations products of cellulose from the different fractions. The glucose content was quantified by GC peak integration with respect to an internal standard.     

Synthesis and S(N)Ar reactions of new dioxins and predioxins

A method for two-step synthesis of dioxin derivatives containing the perfluoropyridine ring has been suggested. It consists of the preparation of corresponding predioxin in the first stage and its cyclization in the next stage. A number of new predioxins have been synthesized using the interaction of polyhalogenpyridines with pyrocatechin and its 4,5-dihaloid derivatives. Formation of dioxins on the basis of not very active arenes occurs smoothly without the necessity for the isolation of predioxin intermediates. For the first time, an interaction of polyhalogenpyridine-containing dioxins and predioxins with nucleophiles of various types (alkyl and arylamines, propylenediamine, hydroxyl anion, and ammonia) has been studied. It was shown that the pyridine fragment does not change the fundamental rules of orientation influence of substituents detemined for non-heterocyclic polyfluorinated arenes. The presence of the labile fluorine atoms reveals a possibility for various modifications of dioxins and predioxins.     

Analysis of organic and inorganic species on the surface of atmospheric aerosol using time-of-flight secondary ion mass spectrometry (TOF-SIMS)

This work explores the utility of time-of-flight static secondary-ion mass spectrometry (TOF-SIMS) for the analysis of the surface organic layer on individual atmospheric aerosol particles. The surface sensitivity and minimal fragmentation available with TOF-SIMS suggest that it can be a powerful tool for the examination of the organic and inorganic species on the surface of individual particles. Cascade impactors were used to collect aerosol from summer 2000 Montana forest fires, winter snowmobile samples in Yellowstone National Park, Hawaiian lava and sea salt, from an Asian Dust event reaching Salt Lake City, Utah in April 2001 and from Salt Lake Valley summer urban aerosol. TOF-SIMS analysis and multivariate statistical techniques combined gave chemical and morphological information about the particles. Surfaces of the aerosol from forest fires, snowmobile exhaust, and sea salt were all dominated by aliphatic hydrocarbons and their amphiphilic derivatives. Each source showed a different organic chemical signature. The extent and composition of the organics layer which typically covers the surface of atmospheric particles are expected to effect all of the surface related aerosol properties such as health effects, the ability of the particle to activate and form cloud droplets, and the aggregation of particles as well as reactions between the particle and gas phase species.     

Identification and estrogenic characterization of impurities in commercial bisphenol A diglycidyl ether (BADGE)

A sample of commercial BADGE was fractioned by HPLC and eight impurities including novel propyl derivatives (2), (5) and (6) were identified by NMR spectrometry, FAB-MS and GC-MS. The estrogenicity, both agonist and antagonist, of fractions containing these impurities was measured with a yeast two-hybrid assay incorporating the human (hER alpha) and a competitive binding assay for hER alpha (ELISA). In the yeast two-hybrid assay, estrogenic antagonist activity was found in two fractions, while estrogenic agonist activity was not found in any. In the ELISA method, the binding affinity to hER alpha was found in three fractions. It is probable that a comprehensive assessment of the estrogenic properties of commercial BADGE, and their implications for human health, will require examination of all its components as described here.     

Levoglucosan,a tracer for cellulose in biomass burning and atmospheric particles

The major organic components of smoke particles from biomass burning are monosaccharide derivatives from the breakdown of cellulose, accompanied by generally lesser amounts of straight-chain, aliphatic and oxygenated compounds and terpenoids from vegetation waxes, resins/gums, and other biopolymers. Levoglucosan and the related degradation products from cellulose can be utilized as specific and general indicator compounds for the presence of emissions from biomass burning in samples of atmospheric fine particulate matter. This enables the potential tracking of such emissions on a global basis. There are other compounds (e.g. amyrones, friedelin, dehydroabietic acid, and thermal derivatives from terpenoids and from lignin—syringaldehyde, vanillin, syringic acid, vanillic acid), which are additional key indicators in smoke from burning of biomass specific to the type of biomass fuel. The monosaccharide derivatives (e.g. levoglucosan) are proposed as specific indicators for cellulose in biomass burning emissions. Levoglucosan is emitted at such high concentrations that it can be detected at considerable distances from the original combustion source.     

The three-dimensional structure of 3,3',4,4'-tetrachlorobiphenyl, a dioxin-like polychlorinated biphenyl (PCB)

The crystal structure of PCB 77 (3,3',4,4'-tetrachlorobiphenyl, C(12)H(6)Cl(4)), a dioxin-like PCB congener, is described. The dihedral angle of PCB 77 is 43.94(6) degrees, which is slightly larger than calculated or experimental dihedral angles of biphenyl derivatives in solution but smaller than experimental dihedral angles in the gas phase.     

Abiotic reduction of antimony(V) by green rust (Fe(4)(II)Fe(2)(III)(OH)(12)SO(4).3H(2)O)

Green rust (Fe(4)(II)Fe(2)(III)(OH)(12)SO(4).3H(2)O) is an intermediate phase in the formation of iron (oxyhydr)oxides such as goethite, lepidocrocite, and magnetite. It is widely considered that green rust occurs in many soil and sediment systems. Green rust has been shown to reduce sorbed Se(VI), Cr(VI), and U(VI). In addition, it is also reported that green rust does not reduce As(V) to As(III). In this study, we have investigated for the first time the interaction between Sb(V) and green rust using XAFS and HPLC-ICP-MS. Most of the added Sb(V) was adsorbed on green rust, and Sb(III), a reduced form, was observed in both solid and liquid phases. Thus, it was shown that green rust has high affinity for Sb(V), and that Sb(V) was reduced to more toxic Sb(III) by green rust despite the high stability of the Sb(V) species even under reducing condition as reported in previous studies. Therefore, green rust can be one of the most important reducing agents for Sb(V), which can influence the Sb mobility in suboxic environments where green rust is formed.     

OH-initiated oxidation of DMS/DMSO: reaction products at high NOx levels

Dimethylsulphide (DMS) gas phase oxidation with OH radicals was investigated by long path FT-IR spectroscopy and by ion chromatography (IC) and HPLC-MS2 to quantify the reaction products and evaluate heterogeneous processes. The experiments were performed considering two different NOx (NO2+NO) levels. The initial concentration of NO2 was varied from 24 ppbV (NOx=1 ppmV) to 953 ppbV (NOx=10 ppmV). Photolysis of H2O2 was used as the OH-radical source. SO2, dimethylsulphoxide (DMSO), dimethylsulphone (DMSO2), methanesulphonic acid (MSA), methanesulphinic acid (MSIA) and methane sulphonyl peroxynitrate (MSPN) were identified as the main sulphur-containing products. The results indicate that higher NOx levels play a significant role in the chemistry of CH3S(O)x radical, influencing both the SO2/MSPN ratio and the amount of the sulphur species in the condensed phase, and that the NO2/NO ratio could influence the trends in the molar yields of the different products. For this reason the NOx content results a limiting parameter when on measure DMS in atmospheric environment.