Occurrence, distribution, and ecological risks of polyhalogenated carbazoles in sediments from Daya Bay and Pearl River Estuary, China.

Polyhalogenated carbazoles (PHCZs) are a group of emerging organic pollutants attracting increasing concern. In this study, 32 sediment samples were collected from the Pearl River Estuary (PRE) and adjacent Daya Bay (DYB) in China and were investigated for the occurrence and distribution of PHCZs. Total concentration of sedimentary PHCZs (∑PHCZs) ranged from 0.79 to 3.08 ng/g in PRE and 0.89 to 1.95 ng/g in DYB, both containing 3,6-dichlorocarbazole as the main component. Higher concentrations of ∑PHCZs were found in the rivers-mouth and inner part of the PRE indicating their main origins from anthropogenic activities. Notably, concentrations of brominated carbazoles (BCZs) gradually increased offshore, which suggests the potential bio-transformation of BCZs under a saline environment. The toxic equivalent of PHCZs was estimated at 0.13-0.34 pg TEQ/g suggesting limited dioxin-like effects on local organisms.

Occurrence of polyhalogenated carbazoles and the combined effects with heavy metals on variation in bacterial communities in estuarine sediments.

Carbazole (CZ) and eight polyhalogenated carbazoles (PHCZs) were quantified by GC-MS in sediments of 12 estuaries, the interface linking large industrial and living areas to the Bohai Sea, China. These pollutants, heavy metals, and environmental factors caused integrated exposure to sediment bacteria. Four PHCZ congeners were detectable, with ΣPHCZs ranging from 0.56 to 15.94 ng/g dw. The dominant congeners were 3,6-dichlorocarbazole (36-CCZ) and 3-chlorocarbazole (3-CCZ), with a mean contribution of 72.6 % and 20.2 %. Significant positive correlations were found between 36-CCZ and both total organic carbon and heavy metals. Redundancy analysis of microbial variation implicated no impacts from PHCZs. Correlation analysis demonstrated an increase in abundance of Rhodocyclaceae but a decrease in Bacteroides-acidifaciens-JCM-10556 with presence of PHCZs, suggesting that these bacteria can be used as potential contamination indicators. The combined exposure of heavy metals, nutrients, and PHCZs may also increase toxicity and biological availability, adversely affecting the ecosystem and human health.

Tissue-specific accumulation, depuration and histopathological effects of 3,6-dichlorocarbazole and 2,7-dibromocarbazole in adult zebrafish (Danio rerio).

Although polyhalogenated carbazoles have been detected with increasing frequency in aquatic ecosystems, their bioaccumulation in fish and corresponding pathological effects related to bioaccumulation are still unclear. Here, we investigated the tissue-specific accumulation, depuration, and histopathological effects of two typical PHCZs, 3,6-dichlorocarbazole (36-CCZ) and 2,7-dibromocarbazole (27-BCZ), in adult zebrafish at three levels (0, 0.15 µg/L (5 × environmentally relevant level), and 50 µg/L (1/10 LC50). The lowest concentrations of 36-CCZ (1.2 µg/g ww) and 27-BCZ (1.4 µg/g ww) were observed in muscle, and the greatest concentrations of 36-CCZ (3.6 µg/g ww) and 27-BCZ (4 µg/g ww) were detected in intestine among the tested tissues. BCFww of 36-CCZ and 27-BCZ in zebrafish ranged from 172.9 (muscle) to 606.6 (intestine) and 285.2 (muscle) to 987.5 (intestine), respectively, indicating that both 36-CCZ and 27-BCZ have high potential of bioaccumulation in aquatic system. The 0.15 µg/L level of 36-CCZ or 27-BCZ caused lipid accumulation in liver, while 50 µg/L of 36-CCZ or 27-BCZ induced liver lesions such as fibrous septa, cytolysis, and nuclear dissolution. Brain damage such as multinucleated cells and nuclear solidification were only observed at 50 µg/L of 27-BCZ. This study provided valuable information in assessing the health and ecological risks of 36-CCZ and 27-BCZ.

Analysis of polyhalogenated carbazoles and two related compounds in earthworms using a modified QuEChERS method with GC/MS and GC/MS/MS.

A precise analytical method based on QuEChERS has been proposed for the concurrent determination of 11 polyhalogenated carbazoles (PHCZs), benzocarbazole (BZCZ), and 9H-carbazoles (CZ). The quantification was confirmed by gas chromatography using triple quadrupole tandem mass spectrometry (Shimadzu GC-MS/MS-TQ8040) and gas chromatography coupled mass spectrometry (Agilent 7890A-5973 GC-MS). The developed method was validated by testing the following parameters: linearity, instrument limit of detection (LOD), instrument limit of quantification (LOQ), method limit of detection (MLD), method limit of quantification (MLQ), matrix effect (ME), accuracy, and precision. All compounds showed good linearity in the range of 0.005-0.2 µg/mL with correlation coefficients higher than 0.992. The method demonstrated satisfactory recoveries (ranging from 71.21 to 105.04%) for most of the compounds with relative standard deviation precision (RSD) < 10.46%, except 3-BCZ (Recovery = 67.53%, RSD = 2.83%). The values of LOD and LOQ varied from 0.05 to 0.24 ng and 0.14 to 0.92 ng, respectively, while those of MLD and MLQ ranged from 0.02 to 0.12 ng/g wet weight (ww) and 0.07 to 0.45 ng/g ww, respectively. The developed method represents a reliable tool for the routine analysis of PHCZ congeners in invertebrate animals.

Analysis of a novel strain Brevundimonas KX-1 capable of degrading 3-chlorocarbazole based on the whole genome sequence.

In this study, a strain was isolated from a sewage treatment plant in Jiangsu Province, China. The strain was identified as Brevundimonas sp. KX-1. After 5 days, 50.2% 3-chlorocarbazole (3-CCZ) was degraded under the optimum condition as follows: 1 g/L starch, 30 °C, pH 6.5 and 50 mg/L 3-CCZ. The degradation of 3-CCZ by KX-1 conformed to the first-order kinetic model under different initial concentrations in this experiment. The intermediate product of 3-CCZ degradation was identified as (2E,4Z)-6-(2-amino-5-chlorophenyl)-2-hydroxy-6-oxohexa-2,4-dienoic acid. The activities of the meta-cleavage enzymes for biphenyl-2,3-diol (the analogs of intermediate product 2'-amino-5'-chloro-[1,1'-biphenyl]-2,3-diol) were measured with the crude extracts of cells grown in the presence of 3-CCZ. The complete genome of KX-1 was sequenced and compared with the Brevundimonas diminuta BZC3. BZC3 and KX-1 belonged to the same species, displaying the genetic similarity of 99%. But BZC3 could efficiently degrade gentamicin for the potential microbial function analysis. Compared with BZC3, KX-1 possessed the primary function annotations about transportation and metabolism of amino acids (6.65%) and the transportation and metabolism of carbohydrates (5.96%). In addition, KX-1 was rich in sucrose and starch metabolism pathways (ko00500) compared with the genome of BZC3, indicating the high efficiency of KX-1 for starch utilization during degradation. This article reveals the difference between strain KX-1 and bacteria of the same genus in terms of the whole genome sequence, demonstrating that KX-1 is a novel strain Brevundimonas with the ability to degrade 3-CCZ.

Insight into the formation of polyhalogenated carbazoles during seawater chlorination.

Although polyhalogenated carbazoles (PHCZs) have been widely detected in the marine environment, their origin is far from clear. In this study, the formation of PHCZs in the chlorination of seawater containing carbazole and its derivatives was investigated. A total of 14 PHCZs including six commonly found and eight unknown congeners were identified in the chlorination of seawater with carbazole. In addition, this study for the first time demonstrated the production of common PHCZs from the chlorination of seawater with 3-methyl carbazole and 3-formyl carbazole, especially 1,8-dibromo-3,6-dichlorocarbazole from 3-methyl carbazole. The formation of PHCZs in the reaction resulted from the halogenation of carbazole by reactive chlorine species (RCS) and mainly reactive bromine species (RBS), forming from the oxidation of bromide by RCS. Results also indicated that the reaction followed a successive halogenation pattern. A higher content of free chlorine and bromide facilitated the generation of RBS, while a higher concentration of DOC exhibited an inhibitory effect. The effects of free chlorine, bromide, DOC, and temperature on the formation of PHCZs were congener-specific. Given the widespread use of chlorination in seawater disinfection, seawater chlorination might be a potential source of PHCZs in the marine environment.

Sediment-water distribution and potential sources of polyhalogenated carbazoles in a coastal river locating at a north metropolis, China.

The fate and transformation of PHCZs in the coastal river environment are not yet comprehensively understood. Paired river water and surface sediment were collected, and 12 PHCZs were analyzed to find out their potential sources and investigate the distribution of PHCZs between river water and sediment. The concentration of ∑PHCZs varied from 8.66 to 42.97 ng/g (mean 22.46 ng/g) in sediment and 17.91 to 81.82 ng/L (mean 39.07 ng/L) in river water. 18-B-36-CCZ was the dominant PHCZ congener in sediment, while 36-CCZ was in water. Meanwhile, the logKoc values for CZ and PHCZs were among the first calculated in the estuary and the mean logKoc varied from 4.12 for 1-B-36-CCZ to 5.63 for 3-CCZ. The logKoc values of CCZs were higher than those of BCZs, this may suggest that sediments have a higher capacity for accumulation and storage of CCZs than highly mobile environmental media.

A carbazole-based spherical microporous polymer for the solid-phase extraction of chlorophenols from water and honey samples.

A new carbazole-based spherical microporous polymer (Car-BDA-POP) was fabricated by employing 4,4'-biphenyldicarboxaldehyde (BDA) and carbazole as monomers via a one-step and non-metal catalyst synthetic approach. It was then explored as an adsorbent for solid-phase extraction (SPE) of some chlorophenols (CPs). Under the optimized extraction conditions, the established Car-BDA-POP-based SPE coupled with high-performance liquid chromatography ultraviolet detection showed good linearity in the concentration range of 0.1-200 ng mL-1 for water samples and 5.0-800 ng g-1 for honey samples with the determination coefficients (r2) ≥ 0.9995 for the analytes. The limits of detection (S/N = 3) for the analytes were in the range of 0.03-0.06 ng mL-1 for water samples and 1.50-2.50 ng g-1 for honey samples. The method recoveries varied from 80.0 % to 116 % in spiked real samples, with the relative standard deviations less than 9.6 %. In addition, the possible adsorption mechanism, adsorption kinetics, and adsorption isotherms were also investigated.

Direct photolysis of diclofenac under simulated sunlight: Transformation pathway and biological concerns.

Topical diclofenac gels are frequently applied on human skin and, consequently are exposed to sunlight during outdoor activities. The degradation of diclofenac (DCF) with sunlight exposure is known to occur but the detailed transformation characteristics and biological concerns have not been comprehensively investigated. In the present work, the transformation products during diclofenac photolysis were identified with the aid of ultra-performance liquid chromatography coupled with triple time-of-flight mass spectrometry (UPLC-TripleTOF). Biological concerns, including microtoxicity, genotoxicity, cytotoxicity and antiestrogenicity were examined with multiple in-vitro bioassays. Spearman correlation analysis was conducted to obtain further insight into the contributions of photolysis products to overall biological concerns. The results demonstrated that diclofenac was readily degraded under sunlight to form five main photolysis products via substitution, dechlorination, dehydroxylation, homodimerization and heterodimerization. Products P1, P2 and P5 were reported previously, while two dimer products (P3 and P4) are innovative products and have not been found in prior studies. A significant elevation in the microtoxicity was found during the photolysis of diclofenac, resulting mainly from the carbazole-containing photolysis products P2, P3, P4 and P5. Genotoxicity and antiestrogenicity declined along with the reduction of diclofenac, indicating that no photolysis products were genotoxic or anti-estrogenic. Modest cytotoxicity to the human skin epidermis cell line was observed and attributed to the formation of intermediate species. This outcome highlighted the biological concerns of diclofenac to human health when exposed to sunlight.

Method development for determination of polyhalogenated carbazoles in industrial waste through gas chromatography/triple quadrupole tandem mass spectrometry.

RATIONALE: Polyhalogenated carbazoles (PHCZs) are dioxin-like compounds that are ubiquitous in the environment. However, their unintentional emissions from industrial sources have received little attention and there is no method available for determination of PHCZs in industrial waste. This research develops a method for determination of PHCZs in industrial waste. METHODS: In this research, a glass column packed with activated silica serves as a rapid and efficient clean-up pretreatment for purification. An isotope dilution gas chromatography/triple quadrupole tandem mass spectrometry method was established for simultaneous determination of eleven PHCZs in industrial samples. RESULTS: The regression coefficients of the standard curves for the congeners were all >0.99. The method detection limit ranged from 1.46 to 3.82 ng/mL for liquid samples and from 0.009 to 0.021 ng/g for solid samples. The precision described by the relative standard deviation ranged from 2.4% to 18.4% for liquid samples and from 5.5% to 35.8% for solid samples. The recovery ranges for the liquid and solid samples were 82%-123% and 83%-137%, respectively. 3-Chlorocarbazole (3-CCZ) and 36-dichlorocarbazole (36-CCZ) can be detected in both chemical bottom liquid from vinyl chloride production and fly ash from medical waste incineration by this method. CONCLUSIONS: An efficient method is established for determination of PHCZs from industrial waste. The discovery of 3-CCZ and 36-CCZ highlights the importance of identification of potential industrial sources of PHCZs and clarification of their contribution to environmental risks. Our method could be applied to investigate industrial emission of PHCZs.

Isolation and identification of 1,3,6,8-tetrabromocarbazole - degrading bacteria.

Halogenated carbazoles are a new class of persistent organic pollutants with dioxin-like toxicity, and this study focused on the microbial degradation of 1,3,6,8-tetrabromocarbazole. In this study, a novel 1,3,6,8-tetrabromocarbazole (1,3,6,8-TBCZ) degrading strain TB-1 was isolated from contaminated soil and identified as Achromobacter sp. based on its 16S rRNA gene sequence analysis, morphological, physiological, and biochemical characteristics. The soil sample was collected from a pharmaceutical factory in Suzhou, China. The strain was able to effectively degrade 1 mg L-1 1,3,6,8-TBCZ in 7 d at pH 7.0 and 30 °C with 80% degradation rate. During the process, the intermediate metabolites were identified as Tribromocarbazole, dibromocarbazole and bromocarbazole via gas chromatography mass spectrometry (GC-MS). The results indicated that strain TB-1 may contribute to the bioremediation of polyhalogenated carbazoles (PHCs) in contaminated environment.

Occurrence and distribution of polyhalogenated carbazoles in eastern Tibetan Plateau soils along the slope of Mt. Qionglai.

Polyhalogenated carbazoles (PHCZs), are considered as potential persistent organic pollutants (POPs), which have been frequently detected in the environment. However, the altitudinal distribution characteristics and possible sources of PHCZs in high mountain soils are still unknown. The present study was the first to analyze PHCZs in soil samples collected along the eastern slope of Mt. Qionglai (MQ), the east edge of the Tibetan Plateau. The concentration of ΣPHCZs (based on dry weight) ranges from 14.4 to 107 ng/g (median value of 40.9), which was at high end of the range reported in soils and sediments to date in the literature. The composition profiles of PHCZs in the soils of MQ were dominated by 3,6-dichlorocarbazole (36-CCZ), 3-chlorocarbazole (3-CCZ), and 2-bromocarbazole (2-BCZ). The mean TOC-normalized concentrations of ΣPHCZs in soil samples from below-treeline (2092 ng/g TOC) were higher than those from alpine meadow (1124 ng/g TOC), probably due to the forest filter effect. The decreasing trend of the PHCZs TOC-normalized concentrations with altitude shows that accumulation of PHCZs from the alpine meadow samples was not affected by the mountain cold-trapping effect. Significantly positive correlations were observed between the concentrations of more than half of detected PHCZ congeners and TOC. In addition, PHCZs show the potential to represent a class of POPs with the frequent occurrence and wide distribution, as the abundance and environmental behavior of PHCZs are similar to some POPs in MQ.

Quantitative Analysis of Bioactive Carbazole Alkaloids in Murraya koenigii (L.) from Six Different Climatic Zones of India Using UPLC/MS/MS and Their Principal Component Analysis.

Murraya koenigii (L.) Spreng (Curry leaf) is a commercially important medicinal plant in South Asia, containing therapeutically valuable carbazole alkaloids (CAs). Thus, the quantitative evaluation of these compounds from different climatic zones of India are an important aspect for quality assessment and economic isolation of targeted compounds from the plant. In this study, quantitative estimation of CAs among 34 Indian natural populations of M. koenigii was assessed using UPLC/MS/MS. The collected populations represent the humid subtropical, tropical wet & dry, tropical wet, semi-arid, arid, and montane climatic zones of India. A total of 11 CAs viz. koenine-I, murrayamine A, koenigine, koenimbidine, koenimbine, O-methylmurrayamine A, girinimbine, mahanine, 8,8''-biskoenigine, isomahanimbine, and mahanimbine were quantified using multiple reaction monitoring (MRM) experiments within 5.0 min. The respective range for natural abundance of CAs were observed as 0.097-1.222, 0.092-5.014, 0.034-0.661, 0.010-1.673, 0.013-7.336, 0.010-0.310, 0.010-0.114, 0.049-5.288, 0.031-1.731, 0.491-3.791, and 0.492-5.399 mg/g in leaves of M. koenigii. The developed method shown linearity regression coefficient (r2 >0.9995), LOD (0.003-0.248 ng/mL), LOQ (0.009-0.754 ng/mL), and the recovery was between 88.803-103.729 %. The bulk of these CAs were recorded in their highest concentrations in the humid subtropical zone, followed by the tropical wet & dry zones of India. Further, principal component analysis (PCA) was performed which differentiated the climatic zones according to the dominant and significant CAs contents within the populations. The study concludes that the method established is simple, rapid, with high sample throughput, and can be used as a tool for commercial purposes and quality control of M. koenigii.

High throughput extraction strategy for simultaneous analysis of 19 tetrabromobisphenol A and halogenated carbazole analogs in seafood.

Tetrabromobisphenol A (TBBPA), halogenated carbazole (HCZ), and their analogs are the emerging pollutants invading the marine environment. So far, a few methods have been reported for the simultaneous analysis of these pollutants due to their large polarity difference. In this study, an effective extraction and cleanup strategy was developed for the simultaneous determination of 19 TBBPA and HCZ congeners in seafood. The 19 analytes could be directly analyzed through high performance liquid chromatography after ultrasonic extraction (methanol, duplicate ethyl acetate-acetone (1:1, v/v)) and gel permeation chromatography cleanup. The acceptable spike-recoveries were within 65.7-118.3%; the precision was intra-/inter-day RSDs: 0.0-6.7%/0.0-8.5%; and the matrix effects were between -14.1% and 12.4%. The detection limits and quantification limits were 0.002-0.014 and 0.020-0.200 µg g-1 dw, respectively. Additionally, this method successfully analyzed the seafood samples and the concentrations of these analytes were in range of nd-5.4 µg g-1 dw.

Occurrence and partitioning of polyhalogenated carbazoles in seawater and sediment from East China Sea.

Polyhalogenated carbazoles (PHCZs) have received great concern due to their environmental persistence and potential dioxin-like toxicities. Their presence in the marine sediment had been well characterized, but limited studies had investigated their environmental behaviors in the marine environment. In this study, we collected paired seawater (n = 48) and surface sediment samples (n = 48) from East China Sea and analyzed for carbazole (CZ) and 11 PHCZs to investigate the occurrence and spatial distribution of CZ and PHCZs in seawater and sediment, as well as to explore the partitioning behaviors of CZ and PHCZs between seawater and sediment. In seawater samples, CZ and nine PHCZs were detected, with the concentrations of ∑PHCZs ranging from 0.21 to 11 ng/L (mean 2.7 ng/L). CZ (94%), 3-CCZ (89%), 1368-CCZ (65%), and 36-CCZ (57%) had relatively higher detection frequencies. Among PHCZs, 36-CCZ (mean 1.1 ng/L) had the highest mean seawater concentration, followed by 3-CCZ (0.51 ng/L) and 1368-CCZ (0.19 ng/L). In sediment, CZ and 11 PHCZs were detected, with the concentrations of ∑PHCZs ranged from 0.34 to 2.0 ng/g (mean 1.0 ng/g). CZ, 3-CCZ, 3-BCZ, 36-CCZ, 27-BCZ, and 36-BCZ were measurable in all sediment samples, and 36-CCZ was the predominant PHCZ (0.47 ng/g, 0.025-1.1 ng/g), followed by 1368-BCZ (0.16 ng/g,

Distribution characteristics and risk assessment of polyhalogenated carbazoles in sea water of the Yellow Sea.

Polyhalogenated carbazoles (PHCZs), a novel type of organic pollutants with dioxin-like toxicity, have gained increasing attention in the past several years. In this study detection and distribution of five PHCZ compounds found in the Yellow Sea region are studied. The range of ∑PHCZ in the detection area is 0.062-0.322 ng/L (median: 0.112 ng/L), with 3,6-dichlorocarbazole and 3,6-dibromocarbazole content being the greatest, ranging from 0.035-0.269 ng/L and 0.010-0.682 ng/L, respectively, followed by 3-CCZ (0.010-0.020 ng/L). The relative toxicity of PHCZs is evaluated by the toxicity equivalent (TEQ), in which a range of 0-0.19 pgTEQ/L (median: 0.006 pgTEQ/L) is determined. According to the results, PHCZs are widely distributed in Yellow Sea water with relatively lower toxicity, and the impact of natural factors, as well as their potential sources, are discussed in order to provide basic scientific data for the investigation of PHCZs in seawater.

Morphological and physiological characterization of filamentous Lentzea aerocolonigenes: Comparison of biopellets by microscopy and flow cytometry.

Cell morphology of filamentous microorganisms is highly interesting during cultivations as it is often linked to productivity and can be influenced by process conditions. Hence, the characterization of cell morphology is of major importance to improve the understanding of industrial processes with filamentous microorganisms. For this purpose, reliable and robust methods are necessary. In this study, pellet morphology and physiology of the rebeccamycin producing filamentous actinomycete Lentzea aerocolonigenes were investigated by microscopy and flow cytometry. Both methods were compared regarding their applicability. To achieve different morphologies, a cultivation with glass bead addition (Ø = 969 µm, 100 g L-1) was compared to an unsupplemented cultivation. This led to two different macro-morphologies. Furthermore, glass bead addition increased rebeccamycin titers after 10 days of cultivation (95 mg L-1 with glass beads, 38 mg L-1 without glass beads). Macro-morphology and viability were investigated through microscopy and flow cytometry. For viability assessment fluorescent staining was used additionally. Smaller, more regular pellets were found for glass bead addition. Pellet diameters resulting from microscopy followed by image analysis were 172 µm without and 106 µm with glass beads, diameters from flow cytometry were 170 and 100 µm, respectively. These results show excellent agreement of both methods, each considering several thousand pellets. Furthermore, the pellet viability obtained from both methods suggested an enhanced metabolic activity in glass bead treated pellets during the exponential production phase. However, total viability values differ for flow cytometry (0.32 without and 0.41 with glass beads) and confocal laser scanning microscopy of single stained pellet slices (life ratio in production phase of 0.10 without and 0.22 with glass beads), which is probably caused by the different numbers of investigated pellets. In confocal laser scanning microscopy only one pellet per sample could be investigated while flow cytometry considered at least 50 pellets per sample, resulting in an increased statistical reliability.

Distribution and ecotoxicological effects of polyhalogenated carbazoles in sediments from Jiaozhou Bay wetland.

A suite of eight polyhalogenated carbazole (PHCZ) congeners were detected in sediments of the Jiaozhou Bay wetland. 3,6-dichlorocarbazole (36-CCZ), and 3,6-dibromocarbazole (36-BCZ) were detected in all samples. The concentrations of ΣPHCZs ranged from 6.9 to 33.4 ng/g dry weight (dw). The recovery of surrogate standard ranged from 85 to 109%. Significant relationships were found between the concentrations of 36-CCZ and those of the other three detected compounds (36-BCZ, 36-ICZ, and 1368-BCZ). However, with regard to the other chemicals, only 1368-BCZ was related to 36-ICZ. The toxic equivalent (TEQ) was used to assess the relative toxicity of PHCZs, which ranged within 0.1-3.9 pg TEQ/g dw in sediment. The inventory of ΣPHCZs was 58.9 kg. These results indicate that PHCZs are widely distributed in the Jiaozhou wetland and the dyeing and finishing industries may be important contamination sources of PHCZs.

Method development for analyzing ultratrace polyhalogenated carbazoles in soil and sediment.

In the past few years, polyhalogenated carbazoles (PHCZs) have been of increasing concern because their structure is similar to that of legacy POPs. In the present study, an analytical method, including intensive cleanup and fractionation procedures in combination with instrumental parameters, was developed to determine ultratrace polyhalogenated carbazoles (PHCZs) in soil and sediment. The eluting sorbents, volume and packing of the column were optimized. Our results showed that 5 g of florisil and 4 g of silica gel under 150 mL of hexane/DCM = 3:1 presented good performance in terms of recovery and repeatability. GC-HRMS, GC-MS/MS (EI-MRM) and GC-MS (EI-SIM) were applied to compare the performance of PHCZ analysis. For sensitivity, EI-MRM presents method detection limits comparable to those of GC-HRMS and much lower than those of EI-SIM. Regarding selectivity, GC-HRMS performed better than the other two techniques since GC-HRMS can reduce interference from perfluorokerosene (PFK) and DDX (DDT, DDE, and DDD) due to its high resolution. GC-HRMS was then further optimized by shortening the run time and modifying the SIM ion. The final method was successfully applied to determine PHCZs in soil and sediment, and the target compounds had almost 100% detection frequency in the samples. The ubiquitous presence of PHCZ in soil and sediment calls for a further investigation of its source, distribution and degradation in the environment.

Polyhalogenated Carbazoles in Surface Sediment from Sanmen Bay, East China Sea: Spatial Distribution and Congener Profile.

Polyhalogenated carbazoles (PHCZs) have recently emerged as a group of halogenated pollutants with broad occurrences and bioaccumulation potential in aquatic systems. However, investigations on their occurrences in coastal waters remain very limited. In the present study we investigated PHCZs in surface sediment collected from 29 sites in Sanmen Bay, East China Sea. The results demonstrated a universal presence of PHCZs in sediment, with concentrations of ∑PHCZs (including all congeners) ranging from 7.7 to 17.5 ng/g dry weight (median: 11.3 ng/g dw). The PHCZ congener composition profile revealed a dominance of 3,6-dichlorocarbazole (36-CCZ) with comparable concentration with that of carbazole. Given that PHCZs are widely distributed in Sanmen Bay sediment and their concentrations rivaled other well-known persistent organic pollutants in the same area, this group of halogenated pollutants merits additional investigations of their potential risks to the studied aquatic system, as well as other important watersheds.