Polyhalogenated Carbazoles In Sediment Research Articles

Environmental behavior and risk of the emerging organic contaminants halogenated carbazoles in chemical industrial park clusters

Polyhalogenated carbazoles (PHCZs) are emerging organic contaminants and have attracted extensive concern because of their widespread occurrence and dioxin-like toxicity. However, the distribution characteristics, environmental behavior, and fate of PHCZs are still poorly understood. In this study, 74 composite environmental samples from 21 Chinese cities were collected around industrial parks in the Yangtze River Delta. The PHCZ concentration ranges in sediment and soil samples were 12.7–5.21 × 103 and 34.6–1.81 × 103 ng/g, respectively, which is equivalent to or higher than those of well-known persistent organic pollutants in the similar areas. The dominant congeners of PHCZs in sediment and soil were 3-chlorocarbazole and 3,6-dichlorocarbazole. Industrial emissions, especially from printing and dyeing textiles, were the main contributors to the high PHCZ environmental concentrations. Potential toxic effects of the PHCZs were evaluated using the toxic equivalent (TEQ) method. The TEQs of PHCZs in sediment and soil were up to 550 and 554 pg TEQ/g dry weight, respectively. The estimated TEQ value of sediment and soil exceeded the corresponding safety guideline, which indicated that PHCZs in the Yangtze River Delta posed high health risks. This study provides an important theoretical basis for controlling and reducing the ecological risks of PHCZs in the chemical industry. At the same time, it also provides reference for the priority control and revision of discharge standards for PHCZs in sewage treatment plants in future.

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.

Development of a three-dimensional porous ionic liquid-chitosan-graphene oxide aerogel for efficient extraction and detection of polyhalogenated carbazoles in sediment samples

The three-dimensional porous ionic liquid-chitosan-graphene oxide aerogel (IL–CS–GOA) monolithic adsorbent with a through-hole structure was prepared using natural chitosan (CS) as the skeletal framework, graphene oxide (GO) as the support to provide mechanical strength, and ionic liquid (IL) as the porogen and modifier. The resulting IL–CS–GOA demonstrated a fluffy and porous structure with various pore sizes and excellent regeneration capability (over six cycles). Its specific surface area exceeded that of CS-GOA and IL-GOA by more than 7 times, enhancing its polyhalogenated carbazoles (PHCZs) adsorption capacity. Within 5 min, IL–CS–GOA (1.0 mg) exhibited adsorption amounts of 539 ng mg−1 for 3-bromocarbazole (3-BCZ), 716 ng mg−1 for 2,7-dibromocarbazole (2,7-BCZ), and 798 ng mg−1 for 1,3,6,8-tetrabromocarbazole (1,3,6,8-BCZ), showcasing its rapid mass transfer and high adsorption capabilities. IL–CS–GOA was utilized as the adsorbent for glass dropper extraction (GDE) in conjunction with gas chromatography-mass spectrometry (GC-MS/MS), to develop a highly efficient and accurate method for determining PHCZs in sediments. Under optimal conditions, the established method exhibited a wide linear range (0.4–250 ng g−1, r ≥ 0.9990), low detection limits (0.04–0.24 ng g−1), and satisfactory recoveries (80.5 %–93.8 %), enabling the accurate and rapid detection of PHCZs in sediment samples. This study presents a novel approach for creating three-dimensional porous aerogels, introduces a new form of sample pretreatment using GDE with a monolithic adsorbent, and offers a new method for the determination of PHCZs in environmental matrices.

Spatial and temporal trends of polyhalogenated carbazoles in sediments of the Yangtze river: insights into the origin

Abstract Fifteen surface sediments and three sediment cores were sampled in the Yangtze River (YR) of China to study the composition and temporal distribution trends of 10 selected polyhalogenated carbazoles (PHCZs) and gained insight into their origin. The total concentrations of PHCZs in the surface sediments ranged from 1.58 to 5.45 ng g−1 dry weight (dw), with an average of 3.11 ng g−1 dw. The composition profiles of PHCZs in the surface sediments were dominated by 1,3,6,8-tetrabromocarbazole, 1,3,6-dibromocarbazole, and 3,6-dichlorocarbazole. The variation trends of PHCZs in the sediment cores showed an apparent peak concentration and subsequently a significant decreasing trend in recent years. A strong correlation existed between PHCZs and sediment physicochemical properties. Furthermore, human activities directly or indirectly affected PHCZ concentrations. The evaluation of the potential toxic effect suggested that the toxic equivalent of PHCZs was less than the safe sediment value.

Spatial and temporal distribution of polyhalogenated carbazoles in sediments from the Yangtze River estuary and adjacent East China Sea

Polyhalogenated carbazoles (PHCZs) have been increasingly detected in marine sediment, raising concerns in recent years. In this study, sediment samples (42 surface and one core) were collected from the Yangtze River estuary and the adjacent East China Sea, and eleven PHCZs and unsubstituted carbazole were measured. The total concentration of PHCZs in surface sediments ranged from 0.19 to 2.49 ng/g dry weight (d.w.) (median 1.03 ng/g d. w.). The congener compositions of PHCZs in the surface sediment were dominated by 3,6-dichlorocarbazole (36-CCZ, 53.2%), followed by 3-chlorocarbazole (14.9%) and 3,6-dibromocarbazole (36-BCZ, 11.8%). Carbazole in the surface sediment ranged from not detected to 9.89 ng/g (median 1.25 ng/g), with a detection frequency of 81.0%. The spatial distribution of 36-CCZ in surface sediments exhibited a clear decline from the coast to offshore, while 36-BCZ showed the opposite trend. The depth profile of 36-CCZ was maintained at a relatively low and stable concentration (about 0.36 ng/g) in core segments from 1903 to 1951, followed by a steady increase to 1.5 ng/g in 2006. This increase coincides with the industrial and agricultural development in China that began in the 1950s. In contrast, the other detected PHCZs and carbazole maintained stable, low concentrations over time. These spatial and temporal patterns suggest that 36-CCZ in this area is predominantly from anthropogenic sources, while 36-BCZ has a natural origin. Toxic equivalent estimations indicated that dioxin-like effects for the observed PHCZs were low. These results provide useful information for understanding the origin of PHCZs and carbazole in this area.

Occurrence and distribution of polyhalogenated carbazoles (PHCs) in sediments from the northern South China Sea

Polyhalogenated carbazoles (PHCs) have been frequently detected in various environments and have gained increasing attention due to their dioxin-like toxicity. In this study, 28 surface sediments and three sediment cores were collected from the northern South China Sea (SCS) to investigate the spatial and temporal distribution trends of PHCs. The total concentrations of PHCs in the surface sediments ranged from 0.25 ng/g to 3.10 ng/g, with a median concentration of 1.50 ng/g. The composition profiles of PHCs in the surface sediments were dominated by 3,6-dichlorocarbazole (36-CCZ), 3,6-dibromocarbazole (36-BCZ), and 1,3,6,8-tetrabromocarbazole (1368-BCZ). The total organic carbon (TOC) based concentrations of 36-CCZ, 1-bromo-3,6-dichlorocarbazole, 1,3,6,8-tetrachlorocarbazole, and 1368-BCZ showed significant positive correlation with water depth (r = 0.58–0.88, p values < 0.01). On the contrary, the TOC based concentration of 2,3,6,7-tetrachlorocarbazole displayed a significant negative correlation with the water depth (r = −0.52, p < 0.01). However, no significant correlation was observed for 3-chlorocarbazole, 36-BCZ, and 1,3,6-tribromocarbazole (p values > 0.05). PHCs in sediment cores showed that congener profiles and concentrations of PHCs remained largely stable throughout the 1890s and 2010s. In addition, all the detected PHCs displayed a significant positive correlation with TOC content of the sediments. These unique spatial and temporal distribution patterns suggest that both terrigenous and natural marine sources contributed the observed PHCs in sediments of the northern SCS.

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.

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 17.5ng/g dry weight (median: 11.3ng/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.

Analysis of polyhalogenated carbazoles in sediment using liquid chromatography–tandem mass spectrometry

The purpose of this study was to develop a novel and sensitive method for the analysis of carbazole and polyhalogenated carbazoles (PHCs) in sediment using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Briefly, 5.0 g of freeze-dried sediment samples were extracted with dichloromethane using pressurized liquid extraction (PLE). The extract was purified with Florisil solid phase extraction cartridge, filtered through 0.22 µm polytetrafluoroethylene filter using a glass syringe, followed by LC-MS/MS analysis. Besides parameters for LC-MS/MS analysis, sample preparation procedures (including solvents for PLE, sorbents for cleanup, and filters for sample filtration) were optimized. The limits of detection and limits of quantification of target compounds were in the ranges of 3.0 × 10−3 to 0.22 ng g−1 dry weight (d.w.) and 1.0 × 10−2 to 0.75 ng g−1 d.w., respectively. The recoveries of target compounds in the spiked sediments at 2.0 ng g−1 d.w. and 10 ng g−1 d.w. were 64.8–91.8% and 70.9–124.7%, respectively, with relative standard deviations being less than 13.2%. Except that 36-BCZ had positive matrix effects of 63.3%, the sediment matrices generally displayed low or medium negative matrix effects on the other target compounds during LC-MS/MS analysis. The developed method was applied in the analysis of carbazoles and PHCs in sediment samples from Jiulong River, Fujian, China and all the target compounds were detected in the samples.