A Non-Bonding Interaction-Based Fluorescent Probe for Detection of Halogenated Carbonyl Compounds.

The fluorescent detection of neutral and volatile carbonyl halogenated compounds had not been studied before. We describe here a simple and sensitive turn-on rhodamin fluorescent probe for the selective detection of fluorinated/brominated/chlorinated/iodinated carbonyl compounds. A wide range of linear or cyclic volatile organic halides was detected with a limit of detection as low as 45.6 nM within 1 min. Mechanistic experiments and DFT calculations indicate the reversible formation of a 1:1 complex of sensor and analyst through non-bonding interaction.

On-line trace monitoring of volatile halogenated compounds in air by improved thermal desorption-gas chromatography-mass spectrometry.

Volatile halogenated compounds (VHCs) are important industrial chemicals and play a crucial role in potential stratospheric ozone-depletion and global warming. Profiling of VHCs is of great significance but replete with challenges due to the species' richness and diversity. In this study, we developed a novel method employing water removal mode combined with thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) for on-line measurement of VHCs at the ultratrace level. By removing water with Nafion dryer tandem cold trap device, VHCs could achieve better separation and identification, and detection precision of VHCs lower than 10%. The proposed method exhibited limits of detection for VHCs ranging from 0.1 to 6.2 pptv. Benefiting from the improved trapping efficiency due to water removal, we successfully quantified 34 VHCs at the Shangdianzi background station and achieved a comprehensive assessment of VHCs in ambient air.

Internal exposure of Flemish teenagers to environmental pollutants: Results of the Flemish Environment and Health Study 2016-2020 (FLEHS IV).

The Flemish Environment and Health Study (FLEHS) collects information on internal exposure to a broad range of environmental chemicals in the general population in Flanders, the Northern region of Belgium. The aim is to establish biomonitoring exposure distributions for the general population in support of public health and environmental policy, environmental risk assessment and risk management decisions. In 2017-2018, urine and blood samples were collected from 428 teenagers by a stratified clustered two stage randomized design. Samples were analyzed for a broad range of biomarkers related to exposure to chlorinated and newer pesticides, brominated and organophosphate flame retardants (BFR/OPFR), polychlorinated biphenyls (PCBs), bisphenols, phthalates and alternative plasticizers, per-and polyfluoroalkyl substances (PFAS), polycyclic aromatic hydrocarbons (PAHs), benzene, metals and trace elements. The geometric mean levels and percentiles of the distribution were estimated for each biomarker, for the whole study population and following stratification for sex, the household educational attainment and the residence area's urbanicity. Geometric means of biomarkers of lead, dichlorodiphenyltrichloroethane (DDT), PCBs, PAHs, regulated phthalates and bisphenol A (BPA) were lower than in the previous FLEHS cycles. Most biomarker levels were below health-based guidance values (HB-GVs). However, HB-GVs of urinary arsenic, blood lead, blood cadmium, sum of serum perfluorooctane sulfonate (PFOS) and perfluoro-1-hexanesulfonate (PFHxS) and the urinary pyrethroid metabolite (3-PBA) were exceeded in respectively 25%, 12%, 39.5%, 10% and 22% of the teenagers. These results suggest that the levels of exposure in the Flemish population to some environmental chemicals might be of concern. At the same time, we noticed that biomarkers for BPA substitutes, metabolites of OPFRs, an expanded list of PFAS, glyphosate and its metabolite could be measured in substantial proportions of participants. Interpretation of these levels in a health-risk context remains uncertain as HB-GVs are lacking. Household educational attainment and residential urbanicity were significant exposure determinants for many biomarkers and could influence specific biomarker levels up to 70% as shown by multiple regression analysis. The research consortium also took care of the broader external communication of results with participants, policy makers, professional groups and civil society organizations. Our study demonstrated that teenagers are exposed to a wide range of chemicals, it demonstrates the success of public policies to reduce exposure but also points to concern and further priorities and needs for follow up.

Asparagopsis Genus: What We Really Know About Its Biological Activities and Chemical Composition.

Although the genus Asparagopsis includes only two taxonomically accepted species, the published literature is unanimous about the invasive nature of this genus in different regions of the globe, and about the availability of large amounts of biomass for which it is important to find a commercial application. This review shows that extracts from Asparagospsis species have already been evaluated for antioxidant, antibacterial, antifungal, antiviral, antifouling, cytotoxic, antimethanogenic and enzyme-inhibitory activity. However, the tables presented herein show, with few exceptions, that the activity level displayed is generally low when compared with positive controls. Studies involving pure compounds being identified in Asparagopsis species are rare. The chemical compositions of most of the evaluated extracts are unknown. At best, the families of the compounds present are suggested. This review also shows that the volatile halogenated compounds, fatty acids and sterols that are biosynthesized by the Asparagopsis species are relatively well known. Many other non-volatile metabolites (halogen compounds, flavonoids, other phenolic compounds) seem to be produced by these species, but their chemical structures and properties haven'been investigated. This shows how much remains to be investigated regarding the secondary-metabolite composition of these species, suggesting further studies following more targeted methodologies.

Fermentative Production of Halogenated Tryptophan Derivatives with Corynebacterium glutamicum Overexpressing Tryptophanase or Decarboxylase Genes.

The aromatic amino acid l-tryptophan serves as a precursor for many valuable compounds such as neuromodulators, indoleamines and indole alkaloids. In this work, tryptophan biosynthesis was extended by halogenation followed by decarboxylation to the respective tryptamines or cleavage to the respective indoles. Either the tryptophanase genes tnaAs from E. coli and Proteus vulgaris or the aromatic amino acid decarboxylase genes AADCs from Bacillus atrophaeus, Clostridium sporogenes, and Ruminococcus gnavus were expressed in Corynebacterium glutamicum strains producing (halogenated) tryptophan. Regarding indoles, final titers of 16 mg L-1 7-Cl-indole and 23 mg L-1 7-Br-indole were attained. Tryptamine production led to a much higher titer of 2.26 g L-1 upon expression of AADC from B. atrophaeus. AADC enzymes were shown to be active with halogenated tryptophan in vitro and in vivo and supported production of 0.36 g L-1 7-Br-tryptamine with a volumetric productivity of 8.3 mg L-1 h-1 in a fed-batch fermentation.

Metagenomics Combined with Stable Isotope Probe (SIP) for the Discovery of Novel Dehalogenases Producing Bacteria.

Halogenated compounds are one of the largest groups of environmental-hazardous chemicals. The removal of the halogen atom from the substrate is possible by the catalytic activity of a type of enzyme called dehalogenase. Hydrolytic dehalogenases are suggested to be a good biodegradation catalyst for halogenated compounds with potential bioremediation applications. Therefore, the identification of possible bacterial strains that produce dehalogenase is of great importance. Soil microorganisms that are regularly exposed to halogenated pesticides are a major source of hydrolytic dehalogenase. Their proper identification may be useful in the production of high-quality dehalogenase. DNA stable isotope probing (DNA-SIP) is quite a useful technique for the identification of active microorganisms that assimilate specific carbon substrates and nutrients. Metagenomics combined with a stable isotope probe (SIP) technique could therefore be used to detect bacterial dehalogenases in pesticides exposed agricultural soil.

Identification of novel halogenated naturally occurring compounds in marine biota by high-resolution mass spectrometry and combined screening approaches.

Marine animals, plants or bacteria are a source of bioactive naturally-occurring halogenated compounds (NHCs) such as bromophenols (BPs), bromoanisoles (BAs) and hydroxylated or methoxylated analogues of polybrominated diphenyl ethers (HO-PBDEs, MeO-PBDEs) and bromobiphenyls (HO-BBs, MeO-BBs). This study applied a comprehensive screening approach using liquid chromatography high-resolution mass spectrometry and combining target, suspect and non-target screening with the aim to identify new hydroxylated NHCs which might be missed by commonly applied gas chromatographic methods. 24 alga samples, 4 sea sponge samples and 7 samples of other invertebrates were screened. Target screening was based on 19 available reference standards of BPs, (di)OH-BDEs and diOH-BBs and yielded seven unequivocally identified compounds. 6-OH-BDE47 was the most frequently detected compound with a detection frequency of 31%. Suspect screening yielded two additional compounds identified in alga samples as well as 17 and 8 compounds identified in sea sponge samples of Lamellodysidea sp. and Callyspongia sp., respectively. The suspect screening results presented here confirmed the findings of previous studies conducted on sea sponge samples of Lamellodysidea sp. and Callyspongia sp. Additionally, in Lamellodysidea sp. and Callyspongia sp. 13 and 4 newly identified NHCs are reported including heptabrominated diOH-BDE, monochlorinated pentabrominated diOH-BDE, hexabrominated OH-MeO-BDE and others. Non-target screening allowed the identification of 31 and 20 polyhalogenated compounds in Lamellodysidea sp. and Callyspongia sp. samples, respectively. Based on the obtained fragmentation spectra, polybrominated dihydroxylated diphenoxybenzenes (diOH-PBDPBs), such as hepta-, octa- and nonabrominated diOH-BDPBs, could be identified in both species. To our knowledge, this study is the first report on the environmental presence of OH-PBDPBs.

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.

Asparagopsis armata Exudate Cocktail: The Quest for the Mechanisms of Toxic Action of an Invasive Seaweed on Marine Invertebrates.

The seaweed Asparagopsis armata exhibits a strong invasive behavior, producing halogenated compounds with effective biological effects. This study addresses the biochemical responses to sublethal concentrations of A. armata exudate on the marine snail Gibbula umbilicalis whole body and the shrimp Palaemon elegans eyes and hepatopancreas. Antioxidant defenses superoxide dismutase (SOD) and glutathione-S-transferase (GST), oxidative damage endpoints lipid peroxidation (LPO) and DNA damage, the neuronal parameter acetylcholinesterase (AChE), and the fatty acid profile were evaluated. Results revealed different metabolic responses in both species. Despite previous studies indicating that the exudate affected G. umbilicalis' survival and behavior, this does not seem to result from oxidative stress or neurotoxicity. For P. elegans, the inhibition of AChE and the decrease of antioxidant capacity is concomitant with the increase of LPO, suggesting neurotoxicity and oxidative stress as contributor mechanisms of toxicity for this species. Fatty acid profile changes were more pronounced for P. elegans with a general increase in polyunsaturated fatty acids (PUFAs) with the exudate exposure, which commonly means a defense mechanism protecting from membrane disruption. Nonetheless, the omega-3 PUFAs arachidonic acid (ARA) and docosapentaenoic acid (DPA) increased in both invertebrates, indicating a common regulation mechanism of inflammation and immunity responses.

A Review: Halogenated Compounds from Marine Fungi.

Marine fungi produce many halogenated metabolites with a variety of structures, from acyclic entities with a simple linear chain to multifaceted polycyclic molecules. Over the past few decades, their pharmaceutical and medical application have been explored and still the door is kept open due to the need of new drugs from relatively underexplored sources. Biological properties of halogenated compounds such as anticancer, antiviral, antibacterial, anti-inflammatory, antifungal, antifouling, and insecticidal activity have been investigated. This review describes the chemical structures and biological activities of 217 halogenated compounds derived mainly from Penicillium and Aspergillus marine fungal strains reported from 1994 to 2019.

Solvent-loaded metal-organic framework of type MIL-101(Cr)-NH2 for the dispersive solid-phase extraction and UHPLC-MS/MS analysis of herbicides from paddy field waters.

A novel solvent-loaded dispersive solid-phase extraction (SL-DSPE) method integrated with liquid-phase microextraction (LPME) has been developed by the direct loading of solvent into the pores of a metal-organic framework (MOF), MIL-101(Cr)-NH2. Despite numerous advantages of MOFs, they are usually highly hydrophobic which limits their dispersibility and therefore effective contact with the analytes in aqueous samples. To overcome this and promote its interactions with polar compounds, MIL-101(Cr) was functionalized with -NH2 and loaded with a comparatively polar organic solvent, dichloromethane. The purpose of dichloromethane was to condition the MIL-101(Cr)-NH2, promote LPME of the analytes and facilitate the re-collection of the materials after the extraction. Five chlorophenoxy acid herbicides, including 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, 4-chlorophenoxyacetic acid, 2-(2,4-dichlorophenoxy)propionic acid, and 2-(2,4,5-trichlorophenoxy)propionic acid, were studied and determined by ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). MIL-101(Cr)-NH2 was characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, and surface area measurement. Several extraction parameters were optimized, and under the most favorable conditions, the SL-DSPE-UHPLC-MS/MS method achieved enrichment factors between 25 and 66. Low limits of detection (2.66-19.7 ng·L-1) and wide dynamic working ranges with good linearity (r2 ≥ 0.991) were attained for all analytes. The method was repeatable, with intra- and inter-day relative standard deviations (RSDs) below 4.5 and 7.6%, respectively, for three replicate determinations. The application of SL-DSPE-UHPLC-MS/MS to paddy field waters gave satisfactory relative recoveries ranging between 80.2 and 108%, with RSDs better 8.4%. Several of the CPAs were detected in these samples. Graphical abstract Schematic of the solvent-loaded dispersive solid-phase extraction procedure. By directly loading dichloromethane into the pores of MIL-101(Cr)-NH2, this method improves the extraction capability of the sorbent through the combination of solvent- and sorbent-based microextraction.

Fully automated graphitic carbon nitride-based disposable pipette extraction-gas chromatography-mass spectrometric analysis of six polychlorinated biphenyls in environmental waters.

A fully automated online emulsification-enhanced disposable pipette extraction-gas chromatography-mass spectrometry (EE-DPX-GC-MS) method has been developed for the extraction of six polychlorinated biphenyls (PCBs) from environmental waters. An in-house prepared material, graphitic carbon nitride (g-C3N4), was used as sorbent in a home-packed DPX device. The six PCBs studied include PCB 10, 28, 52, 153, 138 and 180. g-C3N4 was characterized successfully by X-ray diffraction, elemental analysis, scanning electron microscopy, Fourier-transform infrared and Raman spectroscopy. As a C-N analogue of graphite, the two-dimensional structure of g-C3N4 allows rapid analyte adsorption and desorption to take place. With a significant number of nitrogen functionalities in g-C3N4, the material dispersed well in aqueous sample, increasing the active surface area of contact between the sorbent and the sample. When coupled with a pre-emulsification step, PCBs in each portion of sample could be efficiently extracted by g-C3N4 within 20 s of gentle turbulence. Under the most favorable conditions, the automated online EE-DPX-GC-MS method achieved wide dynamic working ranges with good linearity (r2 ≥ 0.998) for all analytes. Limits of detection ranging between 4.35 and 7.82 ng L-1 were attained, with enrichment factors of between 34 and 57 and relative standard deviations (RSDs) for intra- and inter-day precision of ≤ 8.95% and ≤ 12.6%, respectively. Absolute recoveries were between 69.3% and 109%. The fully automated online EE-DPX-GC-MS approach was applied to industrial wastewaters and reservoir waters where good relative recoveries of PCBs of between 89.3% and 105% were obtained, with RSDs ≤ 11.6%.

Enzyme immobilization on glass fiber membrane for detection of halogenated compounds.

Enzyme immobilization using inorganic membranes has enticed increased attention as they not only improve enzyme stability, but also furnish user-friendly biodevices that can be tailored to different applications. Herein, we explored the suitability of the glass fiber membrane for enzyme immobilization and its application for halocarbon detection. For this, halohydrin dehalogenase (HheC) and bovine serum albumin were crosslinked and immobilized on a glass fiber membrane without membrane functionalization. Immobilized HheC exhibited higher storage stability than its free counterpart over 60 days at 4 °C (67% immobilized vs. 8.1% free) and 30 °C (77% immobilized vs. 57% free). Similarly, the thermal endurance of the immobilized HheC was significantly improved. The practical utility of the membrane-immobilized enzyme was demonstrated by colorimetric detection of 1,3-dichloro-2-propanol (1,3-DCP) and 2,3-dibromo-1-propanol (2,3-DBP) as model analytes. Under optimized conditions, the detection limits of 0.06 mM and 0.09 mM were achieved for 1,3-DCP and 2,3-DBP, respectively. The satisfactory recoveries were observed with spiked river and lake water samples, which demonstrate the application potential of immobilized HheC for screening contaminants in water samples. Our results revealed that the proposed frugal and facile approach could be useful for enzyme stabilization, and mitigation of halocarbon pollution.

Evidence for complex sources of persistent halogenated compounds in birds from the south China sea.

Persistent halogenated compounds (PHCs), including dichlorodiphenyltrichloroethane and its metabolites (DDTs), polybrominated diphenyl ethers (PBDEs), alternative brominated flame retardants (ABFRs), and dechlorane plus (DP), were analyzed in muscle of six bird species from the South China Sea. DDTs, with concentrations up to 19,000 ng/g lipid weight (lw), were the dominant contaminants contributing to 66-99% of PHCs in birds. Concentrations of PBDEs, ABFRs, and DP ranged from 1.1 to 130, 0.73-40, and 0.21-2.5 ng/g lw, respectively. Historically pollution of DDTs and flame retardants in surrounding Asian lands were the main sources for PHCs in birds. BDE 209 was the primary PBDE congener in all birds. 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE) and decabromodiphenyl ethane (DBDPE) were the main ABFRs. Anti-DP and p,p'-DDE were the dominating compounds of DP and DDTs, respectively. Only concentrations of BDEs 153, 203, 196, and 207, p,p'-DDE, and p,p'-DDD showed significant and positive correlations with δ15N values in samples. The resident birds, red-footed booby (Sula sula), had much lower levels of p,p'-DDE and most of PBDEs than those in migratory birds from the South China Sea. Results of stable isotope ratios of carbon suggest the highly variable food items for the five migratory bird species. The abundance of DBDPE in red-footed booby might be related with the ingestion of plastic debris, which still warrants further verification.

Optimized characterization of short-, medium, and long-chain chlorinated paraffins in liquid chromatography-high resolution mass spectrometry.

Chlorinated paraffins (CPs), or polychlorinated n-alkanes, form a complex family of chemicals as they exist as mixtures of several thousands of isomers. To facilitate their classification, they are subdivided into short-chains (C10C13, SCCPs), medium-chains (C14C17, MCCPs), and long-chains (C≥18, LCCPs) and further subdivided according to their chlorination degree. Until recently, the most common strategy implemented for their analysis was GC-ECNI-LRMS, with the main disadvantage being the high dependence of the response to the chlorination degree and the incapability of analysing LCCPs. In this work, we developed a method based on liquid chromatography coupled with electrospray ionisation-Orbitrap mass spectrometry (LC-ESI-HRMS) to expand the analysis capabilities of CPs. Although the different physico-chemical properties of CPs have led to compromises on the choice of analytical parameters, the addition of a mixture of DCM/ACN post-column with appropriate LC-ESI(-)-HRMS parameters enabled optimal and simultaneous detection of SCCPs, MCCPs and LCCPs from 10 to 36 carbons in one single injection. The combination of both the optimised LC-ESI parameters and the high resolution of the mass spectrometer (R = 140,000 @200 m/z) allowed separation of CPs signals of interest from unwanted halogenated ones, leading to minimum interferences in the detection. The optimised method was then successfully applied to the characterization of three types of vegetable oil, which were mostly contaminated with MCCPs. Additionally, the implementation of the LCHRMS strategy enabled the identification of highly chlorinated LCCPs in edible oil for the first time at dozens of ng g-1 lw, which demonstrates the need of such comprehensive methods to expand the knowledge about CPs occurrence in food and environmental matrices.

Nationwide assessment of persistent halogenated compounds (PHCs) in farmed golden pompano of China.

Persistent halogenated compounds (PHCs) contamination has become a major concern over the world. Here we investigated occurrence, spatial distributions, congener profiles, as well as health risks of PHCs in farmed golden pompano in China using gas chromatography/mass spectrometry (GC/MS). The concentrations of PCBs, PBDEs and OCPs were in the range of 0.78-4.79 ng/g wet weight (ww), not detected (nd)-1.14 ng/g ww and 1.1-38.8 ng/g ww, respectively. Furthermore, ρ,ρ'-DDT, ο,ρ'-DDT and PCB 101 were the dominant PHC contaminants. The estimated daily intakes of PHCs through consumption of golden pompano were up to 12.86 and 131.34 ng/kg body weight/day based on the mean and 95th concentrations determined in golden pompano, respectively. Risk-based analysis indicates that target PHCs in golden pompano would not pose risks to human. Our study presents the first report of a nationwide survey of PHCs contamination in farmed golden pompano in China.

Graphitic carbon nitride as sorbent for the emulsification-enhanced disposable pipette extraction of eight organochlorine pesticides prior to GC-MS analysis.

Graphitic carbon nitride (g-C3N4) was explored as a sorbent for the emulsification-enhanced (EE) disposable pipette extraction (DPX) of eight organochlorine pesticides (OCPs) from environmental waters. The OCPs, including α-hexachlorocyclohexane, Aldrin, α-Chlordane, Dieldrin, 4,4'-dichlorodiphenyldichloroethylene, 4,4'-dichlorodiphenyldichloroethane, Heptachlor and Heptachlor epoxide (Isomer A), were analyzed by gas chromatography-mass spectrometry. The sorbent g-C3N4 was characterized by elemental analysis, X-ray diffraction, scanning electron microscopy, Fourier-transform infrared and Raman spectroscopy. As a C-N analogue of graphite, g-C3N4 exhibits good water dispersibility and allows easy analyte recovery - a characteristic not commonly observed in carbon-based materials. When applied to DPX, g-C3N4 rapidly establishes strong interactions with the OCPs. Consequently, g-C3N4 displays superior extraction capability in comparison to six other commercial sorbents. An emulsification step prior to DPX was found to enhance the overall extraction efficiency by pre-concentrating the OCPs into the microdroplets of an organic solvent. The microdroplets were then adsorbed onto g-C3N4. Under the most favorable conditions, wide linear responses spanning over two to four orders of magnitudes are established. The limits of detection range between 2.4 ng·L-1 and 46.2 ng·L-1. The method is reproducible (relative standard deviations ≤ 7.4%) and enrichment factors are between 42 and 57. When applied to the analysis of lake and river water samples, EE-DPX-gas chromatography-mass spectrometry exhibits good resilience against matrix interferences. The relative recoveries range between 77.7% and 106.3%. In comparison to other sorbent-based extraction techniques reported for the analysis of OCPs in aqueous samples, EE-DPX utilizes the minimal amount of sample and solvent, and requires the shortest sample preparation time. Graphical abstractSchematic representation of the emulsification-enhanced disposable pipette extraction (DPX) of organochlorine pesticides (OCPs) using graphitic carbon nitride (g-C3N4) as sorbent. Emulsification and DPX work synergistically, thus allowing rapid dissolution of analytes into microdroplets of organic solvent, before being extracted by g-C3N4.

Characterization of the volatile compounds emitted from municipal solid waste and identification of the key volatile pollutants.

Gaseous emissions from municipal solid waste (MSW) have raised many concerns and complaints. Identifying the key volatile pollutants in the complex gaseous emissions from MSW is significant for the efficient mitigation of their odor nuisances and health risks. For this purpose, we present an integrated investigation of the key volatile pollutants in the gaseous emissions of MSW from the perspectives of emission patterns, odor concentrations and health risks. Air samples were collected during four different emission stages of the waste matrix for both chemical and olfactometric analyses. The total chemical concentrations of the volatile compounds in the air samples were in the range of 21.49 mg m-3 to 295.61 mg m-3, and the odor concentrations varied from 1122 ouE m-3 to 17,782 ouE m-3. The odor concentrations in the air samples were well correlated with the odor activity values (OAVs) of sulfur compounds, oxygenated compounds and ammonia (r = 0.922, 0.879 and 0.780, respectively, for n = 17 and p < 0.01). Moreover, from an integrated perspective involving chemical emissions, the proportions of odor concentrations and health risks, ethanol, methyl mercaptan and hydrogen sulfide were identified as the key volatile pollutants in the gaseous emissions from the waste matrix during the airtight storage stage, and dimethyl disulfide, 1,2-dichloroethane and trichloroethylene were the key volatile pollutants during the ventilation stage.

Predicting the potential for organohalide respiration in wastewater: Comparison of intestinal and wastewater microbiomes.

Halogenated compounds such as polychlorinated biphenyl (PCBs) and polybrominated diphenyl ethers (PBDEs) enter wastewater treatment plants (WWTPs) via the sewage system. These organic contaminants partition between the aqueous and the biosolid phase, where the former is discharged as wastewater effluent. Biosolids from a WWTP provide a hydrophobic surface for adsorption and thus the presence and potential growth of organohalide respiring (OHR) bacteria. In this study, the aim was to assess the potential organohalide respiration capacity in wastewater biosolids by investigating actively organohalide respiring bacteria with a focus on organohalide respiration of PCBs and PCE. The results of the biosolids analysis showed increased amounts of products from PCB respiration. Simultaneously, experiments with organohalide respiration of PCE in biosolids samples showed significant decreases PCE concentration after 46 days (28-92%). Subsequently, it was evaluated if the OHR microbial populations in biosolids were similar to those present in intestinal human biofilms by applying a bioinformatic approach. The OHR populations of the communities were analyzed from existing American and Chinese human intestinal microbiomes. The overall groups Proteobacteria, Bacteroides, Actinobacteria, and Firmicutes phyla dominated the microbiomes in all datasets. The OHR groups in biosolids and intestinal biofilms included Dehalogenimonas, Dehalobacter, Desulfitibacter, Desulfovibrio, Sulfurospirillum, Clostridium, and Comamonas. The results of this study showed that several OHR phyla were present in all samples independent of origin. Wastewater and intestinal microbiomes also contained OHR phyla. Overall, the results points towards using bacterial communities in biosolids as indicators of organohalide respiration in wastewater and intestinal microbiomes, which is related to ingestion or halogenated compounds.

A hydrogel composite prepared from alginate, an amino-functionalized metal-organic framework of type MIL-101(Cr), and magnetite nanoparticles for magnetic solid-phase extraction and UHPLC-MS/MS analysis of polar chlorophenoxy acid herbicides.

A regenerable hydrogel composite is described that is comprised of alginate, amino-functionalized metal-organic framework (MIL-101(Cr)-NH2) and magnetite nanoparticles. The composite was characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, vibrating-sample magnetometry and Brunauer-Emmett-Teller measurement. The material was applied to the magnetic solid-phase extraction of six polar chlorophenoxy acid (CPA) herbicides. Specifically, the herbicides clofibric acid, 4-chlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, 2-(2,4-dichlorophenoxy)propionic acid, 2,4,5-trichlorophenoxyacetic acid and 2-(2,4,5-trichlorophenoxy)propionic acid were extracted from environmental aqueous samples and analyzed by ultra-HPLC-tandem mass spectrometry. The abundance of hydroxyl and carboxyl groups on the natural polymer renders alginate a superior hydrophilic coating. It brings the polar acidic herbicides into closer proximity to the porous metal-organic framework. When integrated with MIL-101(Cr)-NH2, the composite material combines the favorable attributes of high hydrophilicity and large adsorption capacity. An orthogonal array design matrix was employed for the optimization of the extraction parameters. Under the most favorable conditions, the method displays a wide linear response and low limits of detection (0.43-16 ng⋅L-1). Precision and reproducibility (with relative standard deviations of ≤13%) are satisfactory. Enrichment factors range between 27 and 107. The composite was applied to the extraction of CPA herbicides from lake and pond water samples. A markedly improved sorbent-based extraction procedure and performance (compared to previous methods) is found. Graphical abstract Schematic of the magnetic solid-phase extraction of polar herbicides using a hydrogel composite as sorbent. The amino-functionalized MIL-101(Cr) and hydrophilic alginate work in synergy resulting in a material which possess favorable attributes of both components that are beneficial for extraction.