A Review: Halogenated Compounds from Marine Actinomycetes.

Marine actinomycetes, Streptomyces species, produce a variety of halogenated compounds with diverse structures and a range of biological activities owing to their unique metabolic pathways. These halogenated compounds could be classified as polyketides, alkaloids (nitrogen-containing compounds) and terpenoids. Halogenated compounds from marine actinomycetes possess important biological properties such as antibacterial and anticancer activities. This review reports the sources, chemical structures and biological activities of 127 new halogenated compounds originated mainly from Streptomyces reported from 1992 to 2020.

Anion Recognition by Neutral and Cationic Iodotriazole Halogen Bonding Scaffolds.

A computational study of the iodide discrimination by different neutral and cationic iodotriazole halogen bonding hosts was carried out by means of Density Functional Theory. The importance of the size of the scaffold was highlighted and its impact observed in the binding energies and intermolecular X···I distances. Larger scaffolds were found to reduce the electronic repulsion and increase the overlap between the halide electron lone pair and the corresponding I-C antibonding orbital, increasing the halogen bonding interactions. Additionally, the planarity plays an important role within the interaction, and can be tuned using hydroxyl to perform intramolecular hydrogen bonds (IMHB) between the scaffold and the halogen atoms. Structures with IMHB exhibit stronger halogen bond interactions, as evidenced by the shorter intramolecular distances, larger electron density values at the bond critical point and more negative binding energies.

Development and validation of a multiclass method for the determination of organohalogen disinfectant by-products in water samples using solid phase extraction and gas chromatography-tandem mass spectrometry.

An analytical method employing solid phase extraction (SPE) and gas chromatography-tandem mass spectrometry (GC-MS/MS) has been developed for quantitative determination of twenty-six organohalogen disinfectant by-products (OXBPs) in water samples. Target analytes include four trihalomethanes (THMs), four iodohalomethanes (I-HMs), one haloacetaldehyde (HAL), six haloketones (HKs), four halonitromethanes (HNMs), and seven haloacetonitriles (HANs). The sample preparation procedure includes pretreatment with ascorbic acid to quench residual oxidants, followed by analyte enrichment using solid-phase extraction. Five SPE sorbents were tested. The best results for the majority of target analytes were obtained using a styrene-divinylbenzene copolymer phase and methyl tert-butyl ether (MTBE) as the elution agent. GC-MS analysis was performed using electron ionization (EI) and selected reaction monitoring (SRM) for analyte detection. The performance of the method was assessed according to the French standard NF T90-210. The method showed LOQs ranging from 3 to 3000 ng L-1. The applicability of the method has been demonstrated by analyzing both river water and tap water samples. The OXBPs detected most often in the tap water were dibromochloromethane (in 100% of the samples, 4.3-4.7 µg L-1), bromodichloromethane (100%, 1.3-1.7 µg L-1), tribromomethane (100%, 0.8-4.4 µg L-1), trichloromethane (100%, 0.6-0.7 µg L-1), dibromoacetonitrile (75%, 0.5-0.9 µg L-1), with dichloroacetonitrile and 1,1,1-trichloro-2-propanone detected at concentrations around the LOQ levels. In the treated river water samples, the only OXBPs measured at levels above the limit of quantification were trichloromethane and 1,1,1-trichloro-2-propanone. To the best of our knowledge, this is the first SPE-GC-MS/MS method enabling the analysis of an extensive list of OXBPs.

[Removal of AOX in Activated Sludge of a Chemical Pharmaceutical Industry with Fenton Oxidation].

This study aimed to remove AOX (adsorbable organic halogens) with Fenton oxidation from activated sludge in a chemical pharmaceutical industry. The influences of H2O2 dosage, Fe2+ dosage and reaction time were investigated, based on which the reaction conditions for AOX removal were optimized, and the reaction mechanism was discussed. The optimized reaction conditions were as follows:0.90 mol·L-1 of H2O2, 0.045 mol·L-1 of Fe2+[n (Fe2+):n (H2O2) of 1:20] and reaction time of 2 h. Under the optimized conditions, 70.7% of AOX in the sludge and 78.5% of AOX in the supernatant were removed. GC-MS analysis revealed that eleven organic halides were detectable in the original sludge. After Fenton reaction, only three organic halides were detectable, and their peak areas were reduced by 40%-50%. Toxic and hazardous non-AOX organic matters such as xylene, diisobutyl phthalate were also effectively removed.

Reactivity of Aryl Halides for Reductive Dehalogenation in (Sea)water Using Polymer-Supported Terpyridine Palladium Catalyst.

A polymer-supported terpyridine palladium complex was prepared. The complex was found to promote hydrodechlorination of aryl chlorides with potassium formate in seawater. Generally, reductive cleavage of aryl chlorides using transition metal catalysts is more difficult than that of aryl bromides and iodides (reactivity: I > Br > Cl); however, the results obtained did not follow the general trend. Therefore, we investigated the reaction inhibition agents and found a method to remove these inhibitors. The polymeric catalysts showed high catalytic activity and high reusability for transfer reduction in seawater.

Cyclotriveratrylene as a new-type stationary phase for gas chromatographic separations of halogenated compounds and isomers.

Cyclotriveratrylene (CTV) is reported here for the first time as stationary phase for capillary gas chromatographic (GC) separations. CTV stationary phase showed weak polarity comparable to the conventional 5% phenyl polysiloxane stationary phase but exhibited different retention behaviours and higher resolution for some of the indicated analytes. Most importantly, CTV stationary phase exhibited preferential selectivity for halogenated compounds, positional and geometrical isomers. Effect of column temperature on retention and thermal stability of CTV column were also investigated. Moreover, CTV capillary column showed good repeatability in terms of run-to-run, day-to-day and column-to-column. The unique physicochemical features and efficient separation ability for analytes of close properties show the potential of CTV as a new-type stationary phase in GC as well as separation science.

Xylanase and laccase based enzymatic kraft pulp bleaching reduces adsorbable organic halogen (AOX) in bleach effluents: a pilot scale study.

In present study, xylanase and laccase were produced in a cost-effective manner up to 10 kg substrate level and evaluated in elemental chlorine free bleaching of Eucalyptus kraft pulp. Compared to the pulp pre-bleached with xylanase (15%) or laccase (25%) individually, the ClO2 savings were higher with sequential treatment of xylanase followed by laccase (35%) at laboratory scale. The sequential enzyme treatment when applied at pilot scale (50 kg pulp), resulted in improved pulp properties (50% reduced post color number, 15.71% increased tear index) and reduced AOX levels (34%) in bleach effluents. The decreased AOX level in effluents will help to meet AOX discharge limits, while improved pulp properties will be value addition to the paper.

Electrochemical removal of haloacetic acids in a three-dimensional electrochemical reactor with Pd-GAC particles as fixed filler and Pd-modified carbon paper as cathode.

The reductive removal of haloacetic acids (HAAs) in a three-dimensional electrochemical continuous reactor with Pd-granular activated carbon (Pd-GAC) particles as fixed filler and Pd-modified carbon paper (Pd-C) as cathode was studied in this research. Pd-C electrode was prepared from PdCl2 via electrodeposition onto carbon paper. Pd-GAC particles were prepared by the impregnation of Pd(2+) ions onto GAC. Efficient electrocatalytic reduction of HAAs in this reactor was exhibited. Effects of current density, initial HHAs concentration, and hydraulic retention time on the HHAs removal were investigated. Under the current density of 0.3 mA/cm(2), HAAs with initial concentration of 120 µg/L were reduced to be less than 60 µg/L with hydraulic retention time of 20 min. Electron transfer and HAAs diffusion both played an important role in controlling the electro-reduction process under the conditions of current density less than 0.6 mA/cm(2) with an initial HAAs concentration ranging from 120 to 600 µg/L. However, the HAAs diffusion became the primary rate-limiting step when the current density was higher than 0.6 mA/cm(2). The Pd(0) and Pd(2+) species were detected by X-ray photoelectron spectroscopy. The stability of the electrochemical reactor in the reduction removal of HAAs was also exhibited.

Antibacterial activity of extracellular compounds produced by a Pseudomonas strain against methicillin-resistant Staphylococcus aureus (MRSA) strains.

BACKGROUND: The emergence of multidrug-resistant bacteria is a world health problem. Staphylococcus aureus, including methicillin-resistant S. aureus (MRSA) strains, is one of the most important human pathogens associated with hospital and community-acquired infections. The aim of this work was to evaluate the antibacterial activity of a Pseudomonas aeruginosa-derived compound against MRSA strains. METHODS: Thirty clinical MRSA strains were isolated, and three standard MRSA strains were evaluated. The extracellular compounds were purified by vacuum liquid chromatography. Evaluation of antibacterial activity was performed by agar diffusion technique, determination of the minimal inhibitory concentration, curve of growth and viability and scanning electron microscopy. Interaction of an extracellular compound with silver nanoparticle was studied to evaluate antibacterial effect. RESULTS: The F3 (ethyl acetate) and F3d (dichloromethane- ethyl acetate) fractions demonstrated antibacterial activity against the MRSA strains. Phenazine-1-carboxamide was identified and purified from the F3d fraction and demonstrated slight antibacterial activity against MRSA, and synergic effect when combined with silver nanoparticles produced by Fusarium oxysporum. Organohalogen compound was purified from this fraction showing high antibacterial effect. Using scanning electron microscopy, we show that the F3d fraction caused morphological changes to the cell wall of the MRSA strains. CONCLUSIONS: These results suggest that P. aeruginosa-produced compounds such as phenazines have inhibitory effects against MRSA and may be a good alternative treatment to control infections caused by MRSA.

Bradbury-Nielsen-gate-grid structure for further enhancing the resolution of ion mobility spectrometry.

In our previous work we proposed a three-zone theory for the Bradbury-Nielsen (BN) gate and proved with a grid-BN structure ion mobility drift tube that enhancements of the three-zone features led to higher resolutions and sometimes higher sensitivities. In this work we continued to seek further improvements of the resolution performance by adopting a BN-grid structure in the same drift tube. The postgate grid works both for confinement of the BN gate induced electric field and for isolation of the injection field from the drift field. This makes it possible to obtain better resolutions by further enhancing the compression electric field and lowering the injection field. It was found in the following experiments that reducing the injection field led to higher resolutions yet lower sensitivities. At an injection field of 140 V/cm, the inverse compression coefficient was found to be much larger than that in the grid-BN structure at all gating voltage differences (GVDs). At GVD = 350 V and a gate pulse width of 0.34 ms, the ion mobility spectrometry efficiency R(m)/R(c) reached as high as 221% in the BN-grid structure, presenting a further increase compared to 182% in the grid-BN structure. Finally, two examples are given to show the separation power improvements with good resolutions.

Is halogen content the most important factor in the removal of halogenated trace organics by MBR treatment?

This study investigated the relationship between physicochemical properties (namely halogen content and hydrophobicity) of halogenated trace organics and their removal efficiencies by a laboratory scale membrane bioreactor (MBR) under stable operating conditions. The reported results demonstrated a combined effect of halogen content and hydrophobicity on the removal. Compounds with high halogen content (>0.3) were well removed (>85%) when they possessed high hydrophobicity (Log D>3.2), while those with lower Log D values were also well removed if they had low halogen content (<0.1). General indices such as the BIOWIN index (which is based on only biodegradation) or a more specific index such as the halogen content (which captures a chemical aspect) appeared insufficient to predict the removal efficiency of halogenated compounds in MBR. Experimental data confirmed that the ratio of halogen content and Log D, which incorporates two important physico-chemical properties, is comparatively more suitable.

Bio-conventional bleaching of wheat straw soda-AQ pulp with crude xylanases from SH-1 NTCC-1163 and SH-2 NTCC-1164 strains of Coprinellus disseminatus to mitigate AOX generation.

Two novel cellulase-poor xylanases from Coprinellus disseminatus SH-1 NTCC-1163 (enzyme-A) and SH-2 NTCC-1164 (enzyme-B) produced under solid-state fermentation mitigated kappa number of wheat straw soda-AQ pulps by 24.38 and 27.94% respectively after XE stages. The release of reducing sugars and chromophores was highest for both the enzymes at 10IU/g and reaction time 180min for 55°C at variable consistencies that is, 10% for enzyme-A and 5% for enzyme-B. (A)XECEHH and (B)XECEHH sequences improved brightness by 5.17 and 2.58% respectively at 4.5% chlorine charge. AOX in (A)XECEHH and (B)XECEHH sequences reduced by 56.11 and 55.75% respectively at 4.5% chlorine charge and 68.34 and 67.98% respectively at 2.25% chlorine charge respectively compared to control. Both the enzymes showed improvement in double fold and tear index with a decrease in burst and tensile index. SEM showed peeling, cracking and delamination in fibers due to enzyme treatment thus facilitating the penetration of bleach chemicals.

Halogenated terpenes and a C(15)-acetogenin from the marine red alga Laurencia saitoi.

Seven parguerane diterpenes: 15-bromo-2,7,19-triacetoxyparguer-9(11)-en-16-ol (1), 15-bromo-2,7,16,19-tetraacetoxyparguer-9(11)-ene (2), 15-bromo-2,19-diacetoxyparguer-9(11)-en-7,16-diol (3), 15-bromo-2,16,19-triacetoxyparguer-9(11)-en-7-ol (4), 15-bromo-2,16-diacetoxyparguer-9(11)-en-7-ol (5), 15-bromoparguer-9(11)-en-16-ol (6), 15-bromoparguer-7-en-16-ol (7), two polyether triterpenes: thyrsiferol (8) and thyrsiferyl 23-acetate (9), and one C(15)-acetogenin, neolaurallene (10), were isolated from a sample of marine red alga Laurencia saitoi collected off the coast of Yantai. Their structures were established by detailed NMR spectroscopic analysis and comparison with literature data.

Study of some UV filters stability in chlorinated water and identification of halogenated by-products by gas chromatography-mass spectrometry.

This work studies the stability of three UV filters: 2-ethylhexyl salicylate (ES), 2-ethylhexyl 4-(dimethylamino) benzoate (EHPABA) and 2-hydroxy-4-methoxybenzophenone (BP-3), in water samples containing low concentrations of free chlorine. Moreover, 2,4-dihydroxybenzophenone (2,4-DHBP), a metabolite of BP-3, was also included in some of the performed assays. Experiments were carried out considering free chlorine and analytes concentrations at the microg mL(-1) and ng mL(-1) level, respectively. Gas chromatography with mass spectrometry was used to follow the time course of target compounds and to identify their halogenated by-products. Concentration of water samples with solid-phase extraction cartridges and derivatization (silylation) of some species were also employed to improve their detectability. Under the experimental conditions explored in this work, ES showed an acceptable stability whereas the rest of species reacted with free chlorine at significant rates following pseudo-first-order kinetics. Their half-lives ranged from 0.4 to 25 min depending on the UV filter, chlorine concentration, water pH and presence of bromide traces. For EHPABA a relatively simple degradation pathway was established. It consisted of aromatic substitution of one atom of hydrogen per chlorine or bromide. The same reaction pattern was observed for BP-3 leading, in this case, to mono- and di-halogenated by-products. In addition, several halogenated forms of 3-methoxyphenol were identified as BP-3 cleavage by-products.

Design of a multifunctional permeable reactive barrier for the treatment of landfill leachate contamination: laboratory column evaluation.

This study describes a laboratory-scale multifunctional permeable reactive barrier (multibarrier) for the removal of ammonium (NH4+: 313 +/- 51 mg N L(-1)), adsorbable organic halogens (AOX: 0.71 +/- 0.25 mg Cl L(-1)), chemical oxygen demand (COD: 389 +/- 36 mg L(-1)), and toxicity from leachate originating from a 40-year-old Belgian landfill. The complexity of the contamination required a sequential setup combining different reactive materials and removal processes. All target contaminants could be removed to levels below the regulatory discharge limits. Ammonium was efficiently removed in a first microbial nitrification compartment, which was equipped with diffusive oxygen emitters to ensure a sufficient oxygen supply. Ammonium was mainly oxidized to nitrite and to a lesser extent to nitrate, with an average mass recovery of 96%. Remaining ammonium concentrations could be further removed by ion exchange in a second compartment filled with clinoptilolite, exhibiting a total ammonium removal capacity of 46.7 mg N per g of clinoptilolite. Athird microbial denitrification compartment fed with sodium butyrate as a carbon source, was used to remove nitrate and nitrite formed in the first compartment. Maximum nitrification and denitrification rates at 12 degrees C indicated that hydraulic retention times of approximately 62 h and approximately 32 h were required in the columns to remove 400 mg N L(-1) by nitrification and denitrification, respectively. Leachate toxicity decreased to background levelstogetherwiththe removal of ammonium and its oxidation products. AOX and COD were efficiently removed by sorption in an additional compartment filled with granular activated carbon.

Treatment of landfill leachate with aerated and non-aerated submerged biofilters.

A submerged biological filter packed with clayey schists from brick industrial waste as support material was used to treat landfill leachate. The pilot-scale plant consisted of two separated reactors, running in aerated and non-aerated conditions respectively. The leachate was taken from a landfill in Granada (southeast Spain) and was considered as partially stabilized with average chemical oxygen demand (COD) concentrations of 18,683.3 mg COD/L. The efficiency of the system at reducing COD, biological oxygen demand (BOD(5)), total suspended solids (TSS), total volatile solids (TVS), total solids (TS), cations and anions concentrations was tested comparing aerating and non-aerating conditions under several volumic organic loadings (15.7, 25.1 and 31.1 kg COD/m(3)d), a hydraulic loading of 0.7 m(3)/m(2)d and an internal recirculation of 250%. Results obtained showed that the aerated reactor was more effective than the non-aerated reactor in the removal of COD, BOD5 and TS, with maximum efficiencies of 66.7%, 91.2% and 21.7%, respectively. The volumic organic loading of 25.1 COD/m(3)d obtained best results. However, for the removal of TSS and TVS the non-aerated reactor showed better results (42%). The behaviour of different cations (Na(+), K(+), and Mg(2+)) and anions (F(-), Cl(-), Br(-)) was also monitored and a reduction in their concentration in the effluent was detected, in the order of 61% for Ca(2+) and 100% for F(-).

Isolation of novel bacteria able to degrade alpha-halocarboxylic acids by enrichment from environmental samples.

In order to isolate novel bacteria able to degrade alpha-halocarboxylic acids a variety of culturing strategies were implemented. Eight pure cultures were obtained and were found to be associated with the Gram negative Proteobacteria and the Gram positive Bacillus and Enterococcus genera. Furthermore, several strains were obtained which were able to degrade the DL-halocarboxylic acids anaerobically. Molecular analysis of the pure cultures led us to conclude that they may possess novel enzymes involved in the biodegradation of the alpha-halocarboxylic acids. These results are the first for nearly 40 years to describe the isolation of Gram positive isolates on an alpha-halocarboxylic acid as the sole source of carbon and energy, which also show the ability to de-toxify the test substrate by releasing chloride.

Group separation of organohalogenated compounds by means of comprehensive two-dimensional gas chromatography.

Separations of 12 compound classes, polychlorinated biphenyls (PCBs), diphenyl ethers (PCDEs), naphthalenes (PCNs), dibenzothiophenes (PCDTs), dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), terphenyls (PCTs) and alkanes (PCAs), toxaphene, organohalogenated pesticides (OCPs), and polybrominated biphenyls (PBBs) and diphenyl ethers (PBDEs) by comprehensive two-dimensional gas chromatography were evaluated. Five column combinations, DB-1 x 007-210, DB-1 x HT-8, DB-1 x LC-50, DB-1 x 007-65HT and DB-1 x VF-23ms were used to study, primarily, group-type separations, but attention was devoted also to within-class separation, especially for those classes which were not addressed in much detail before, the PCNs, OCPs, PBBs and PCTs. The DB-1 x 007-210 column set did not offer any extra separation compared to one-dimensional GC. For the DB-1 x HT-8 column combination, the useful principle of congener separation on the basis of number of halogen substituents in a molecule was confirmed (PCBs, toxaphene) and extended (PCTs, PBDEs). No practically useful group-type separation was observed for this column combination. The DB-1 x LC-50 set provides group separation based on planarity: planar compounds such as PCDDs, PCDFs, PCDTs and PCNs are much more retained than, and therefore separated from, non-planar analytes. Within the classes of PCBs, PBBs and PCTs highly useful separation of planar from non-planar compounds was also observed. The DB-1 x 007-65HT column set effectively separates PCAs and PBDEs from all other compound classes, and provides a good separation of brominated and chlorinated analogue classes from each other. This column set was the most efficient one for within-class separation of OCPs and PCNs. Finally, DB-1 x VF-23ms yields excellent within-class separations, especially of non-aromatic compounds, viz. OCPs, toxaphene and PCAs. No group separation was observed here. The applicability of the approach was demonstrated for a sediment extract and a dust extract. In the sediment extract, PCDDs, PCDFs, PCAs and PCNs were identified and their efficient separation was achieved. In the dust sample, separation of PCAs and PBDEs was achieved and several new PBDE congeners were identified.

Removal of bulk dissolved organic carbon (DOC) and trace organic compounds by bank filtration and artificial recharge.

Bank filtration and artificial recharge provide an important drinking water source to the city of Berlin. Due to the practice of water recycling through a semi-closed urban water cycle, the introduction of effluent organic matter (EfOM) and persistent trace organic pollutants in the drinking water is of potential concern. In the work reported herein, the research objectives are to study the removal of bulk and trace organics at bank filtration and artificial recharge sites and to assess important factors of influence for the Berlin area. The monthly analytical program is comprised of dissolved organic carbon (DOC), UV absorbance (UVA254), liquid chromatography with organic carbon detection (LC-OCD), differentiated adsorbable organic halogens (AOX) and single organic compound analysis of a few model compounds. More than 1 year of monitoring was conducted on observation wells located along the flowpaths of the infiltrating water at two field sites that have different characteristics regarding redox conditions, travel time, and travel distance. Two transects are highlighted: one associated with a bank filtration site dominated by anoxic/anaerobic conditions with a travel time of up to 4-5 months, and another with an artificial recharge site dominated by aerobic conditions with a travel time of up to 50 days. It was found that redox conditions and travel time significantly influence the DOC degradation kinetics and the efficiency of AOX and trace compound removal.