Global environmental and toxicological impacts of polybrominated diphenyl ethers versus organophosphate esters: A comparative analysis and regrettable substitution dilemma.

The prevalence of organophosphate esters (OPEs) in the global environment is increasing, which aligns with the decline in the usage of polybrominated diphenyl ethers (PBDEs). PBDEs, a category of flame retardants, were banned and classified as persistent organic pollutants (POPs) through the Stockholm Convention due to their toxic and persistent properties. Despite a lack of comprehensive understanding of their ecological and health consequences, OPEs were adopted as replacements for PBDEs. This research aims to offer a comparative assessment of PBDEs and OPEs in various domains, specifically focusing on their persistence, bioaccumulation, and toxicity (PBT) properties. This study explored physicochemical properties (such as molecular weight, octanol-water partition coefficient, octanol-air partition coefficient, Henry's law constant, and vapor pressures), environmental behaviors, global concentrations in environmental matrices (air, water, and soil), toxicities, bioaccumulation, and trophic transfer mechanisms of both groups of compounds. Based on the comparison and analysis of environmental and toxicological data, we evaluate whether OPEs represent another instance of regrettable substitution and global contamination as much as PBDEs. Our findings indicate that the physical and chemical characteristics, environmental behaviors, and global concentrations of PBDEs and OPEs, are similar and overlap in many instances. Notably, OPE concentrations have even surged by orders of several magnitude compared to PBDEs in certain pristine regions like the Arctic and Antarctic, implying long-range transport. In many instances, air and water concentrations of OPEs have been increased than PBDEs. While the bioaccumulation factors (BAFs) of PBDEs (ranging from 4.8 to 7.5) are slightly elevated compared to OPEs (-0.5 to 5.36) in aquatic environments, both groups of compounds exhibit BAF values beyond the threshold of 5000 L/kg (log10 BAF > 3.7). Similarly, the trophic magnification factors (TMFs) for PBDEs (ranging from 0.39 to 4.44) slightly surpass those for OPEs (ranging from 1.06 to 3.5) in all cases. Metabolic biotransformation rates (LogKM) and hydrophobicity are potentially major factors deciding their trophic magnification potential. However, many compounds of PBDEs and OPEs show TMF values higher than 1, indicating biomagnification potential. Collectively, all data suggest that PBDEs and OPEs have the potential to bioaccumulate and transfer through the food chain. OPEs and PBDEs present a myriad of toxicity endpoints, with notable overlaps encompassing reproductive issues, oxidative stress, developmental defects, liver dysfunction, DNA damage, neurological toxicity, reproductive anomalies, carcinogenic effects, and behavior changes. Based on our investigation and comparative analysis, we conclude that substituting PBDEs with OPEs is regrettable based on PBT properties, underscoring the urgency for policy reforms and effective management strategies. Addressing this predicament before an exacerbation of global contamination is imperative.

The bioaccumulation and biotransformation of tetrabromobisphenol A bis (allyl ether) in common carp (Cyprinus carpio).

Tetrabromobisphenol A bis (allyl ether) (TBBPA-BAE) is an extensively used brominated flame retardant, which has raised considerable concern because of its neurotoxic and endocrine disruption effects on aquatic organisms. However, previous studies mainly focused on the parent compound before modification, tetrabromobisphenol A (TBBPA), and little information is available about the bioconcentration and biotransformation of TBBPA derivatives in fish. In this study, we investigated the tissue-specific uptake, elimination kinetic, and biotransformation of TBBPA-BAE in common carp (Cyprinus carpio). The fish were exposed to TBBPA-BAE at environmentally relevant concentrations (20 µg·L-1) for 28 days, followed by 14 days of depuration. The results showed TBBPA-BAE could rapidly accumulate in common carp. Among the seven tissues studied, the highest concentrations of TBBPA-BAE were observed in the liver (6.00 µg·g-1 wet weight [ww]) on day 24, while the longest residence time was observed in the kidney (t1/2 values of 18.7 days). Biotransformation of TBBPA-BAE was documented in the in vivo experiments, and 14 different phase I and phase II metabolites were identified in the liver. These findings suggest the biotransformation products of TBBPA-BAE should be considered for a comprehensive risk evaluation.

Development and application of diffusive gradients in thin films for in situ sampling of the organic UV filter 4-methylbenzylidene camphor (4-MBC) in waters.

4-Methylbenzylidene camphor (4-MBC), a typical organic UV filter (OUVF) in personal care products, is considered to be a potential endocrine disruptor due to its estrogenic activity and bioaccumulation. Although 4-MBC residues have been extensively identified in aquatic waters, little is known about their occurrence, levels, and potential risk in coastal waters. This study developed a reliable sampling approach, based on diffusive gradients in thin films (DGT) with XAD-2 as the binding agent, for monitoring 4-MBC in coastal waters. The diffusion coefficients of 4-MBC in freshwater and artificial seawater were 3.65 × 10-6 cm2/s and 3.83 × 10-6 cm2/s, respectively. XAD-2 binding gel showed rapid adsorption to 4-MBC. The accumulated masses of 4-MBC in XAD-2 DGT increased linearly with deployed time for 7 days in freshwater and seawater, which agreed well with theoretical predictions. The sampling performance was independent of ionic strength (0.0001-0.5 M), pH (4.0-8.5), and dissolved organic matter (0-20 mg/L). Field deployment in the river estuary and bathing beach showed that DGT-measured 4-MBC concentrations were consistent in comparison with grab sampling. Environmental risk assessment showed that 4-MBC may pose a medium risk to aquatic organisms based on computed risk quotient (RQ) values. Sewage discharge is the main source of 4-MBC risk, while the residue in recreation beaches contributes more significantly in summer. The established DGT sampling is suitable for seasonal monitoring, source identification, and risk assessment of 4-MBC in coastal waters.

The photoactivity of complexation of DOM and copper in aquatic system: Implication on the photodegradation of TBBPA.

The photoactivity of dissolved organic matter (DOM) has a great impact on the photodegradation of organic pollutants in natural waters. In this study, the photodegradation of TBBPA was investigated under simulated sunlight irradiation in the presence of copper ion (Cu2+), dissolved organic matter (DOM) and Cu-DOM complexation (Cu-DOM) to illustrate the effect of Cu2+ on photoactivity of DOM. The rate of photodegradation of TBBPA in the presence of Cu-DOM complex was 3.2 times higher than that in pure water. The effects of Cu2+, DOM and Cu-DOM on the photodegradation of TBBPA were highly pH dependent and hydroxyl radical(·OH) responded for the acceleration effect. Spectral and radical experiments indicated that Cu2+ had high affinity to fluorescence components of DOM, and acted as both the cation bridge and electron shuttle, resulting the aggregation of DOM and increasing of steady-state concentration of ·OH (·OHss). Simultaneously, Cu2+ also inhibited intramolecular energy transfer leading to the decrease of steady-state concentration singlet oxygen (1O2ss) and triplet of DOM (3DOM⁎ss). The interaction between Cu2+ and DOM followed the order of conjugated carbonyl CO, COO- or CO stretching in phenolic groups and carbohydrate or alcoholic CO groups. With these results, a comprehensive investigation on the photodegradation of TBBPA in the presence of Cu-DOM was conducted, and the effect of Cu2+ on the photoactivity of DOM was illustrated. These findings helped to understanding the potential mechanism of interaction among metal cation, DOM and organic pollutants in sunlit surface water, especially for the DOM-induced photodegradation of organic pollutants.

Influence of habitats and physicochemical factors on trophic transfer processes of antibiotics in a freshwater ecosystem: Application of stable isotopes and human health risks.

Habitats of species and physicochemical factors are of great importance in determining the trophic transfer of contaminants in freshwater ecosystems. There is little information on how multiple physicochemical factors and habitats influence the trophic transfer of antibiotics in freshwater food webs. This study investigated the concentrations of 7 sulfonamides (SAs), 4 fluoroquinolones (FQs), 4 tetracyclines (TCs) and 2 macrolides (MLs) in the Lake Dianshan food web. Stable isotope analysis (SIA), and mathematical models were used to assign trophic levels and distinguish between the benthic food web (BFW) and pelagic food web (PFW). Values of stable nitrogen isotope (δ15N‰) and stable carbon isotope (δ13C‰) ranged from 10.2 ± 0.11 to 19.72 ± 0.05 and -33.67 ± 0.18 to -20.79 ± 0.50, respectively. Total concentrations of antibiotics ranged from 36.63 ± 12.73 ng/g dry weight (dw) to 105.85 ± 12.95 ng/g dw for all species. The relative abundance of antibiotics was in the following order: ∑FQs (36.49 %) > ∑SAs (26.70 %), >∑MLs (12.63 %) for all biotas. Trophic magnification factor (TMFs) values for individual antibiotics ranged from 0.10 to 1.20 and 0.31 to 1.82 for PFW and BFW, respectively. Three classes of antibiotics ∑FQs (p < 0.05), ∑TCs (p < 0.05), and ∑MLs (p < 0.05) showed significant trophic dilution in PFW, opposite to non-significant trophic dilution in BFW. The influence of various physicochemical factors was not strong over trophic transfer (e.g., octanol-water partition coefficient-LogKow (r = -0.05 in PFW, r = -0.14 in BFW) and distribution coefficient-LogD (r = 0.06 in PWF, r = -0.28 in BFW)) except for aqueous solubility (LogS). Results indicated a significantly higher trophic dilution of antibiotics in the PFW than in the BFW. Among the studied six physicochemical factors, only LogS significantly influences (p < 0.05) the trophic transfer of antibiotics in the freshwater food web. Health risk assessments indicated that currently, there were no serious risks present for urban and rural populations.

Citric acid can enhance the uptake and accumulation of organophosphate esters (OPEs) in Suaeda salsa rhizosphere: Potential for phytoremediation.

Bioaccumulation of organophosphate esters (OPEs) by plants has been widely studied, but how root exudates influence their bioavailability to plants is poorly understood. Here, we examined whether root exudates could promote desorption of OPEs, thereby enhancing bioavailability and subsequent accumulation potential. Root exudate components exert great influences on the sorption/desorption isotherms of OPEs in soils, resulting in activating OPEs and enhanced bioavailability. Among root exudate components, citric acid was confirmed to play a crucial role in driving OPEs, with 77.7-90.3 % attribution. Citric acid at rhizosphere levels (0.01-0.4 mM) can successfully reduce OPEs sorption to soils by decreasing electrostatic interaction, ligand exchange, and hydrophobic force. Pot experiments indicated that the addition of citric acid can significantly increase OPEs dissolution and bioaccumulation from the rhizosphere soil to Suaeda salsa. A higher level of citric acid in rhizosphere soil resulted in a higher accumulation of OPEs in Suaeda salsa, which was partly attributed to the enhanced OPEs mobility, and the increased root lengths (13.4-29.0 %) and tip numbers (60.2-120 %), promoting OPEs uptake by roots. Our findings suggest the activation process of OPEs in soils by citric acid at rhizosphere levels and provide insights into designing LMWOAs-enhanced phytoremediation techniques in natural environment.

Development of diffusive gradients in thin film technique for seasonal monitoring of benzophenone-type UV filters in coastal waters.

Benzophenone(BP)-type UV filters are continuously released into various aquatic environments via the effluent discharge of wastewater treatment plants (WWTPs) and recreational activities in coastal beaches. In this study, we developed a robust and reliable sampling approach, diffusive gradients in thin-films (DGT), for seasonal monitoring of six BP derivatives in coastal waters to investigate their occurrence and environmental risk. The binding capacities of both XAD-2 and HLB gels for test BPs were over 252 µg with no significant deterioration in marine environment, suggesting that theoretically, DGT is capable of sampling for at least 3 months effectively. The diffusion coefficients of BPs in freshwater and seawater were determined for the first time. The sampling performance showed no dependence on environmental conditions including pH (4.0-8.5), ionic strength (0.0001-0.5 M) and dissolved organic matter (0-20 mg L-1). The developed DGT samplers were successfully applied in a river estuary linked to a WWTP and a bathing beach at different periods of one year. Results showed that the concentrations of BPs in the coastal waters were dependent on seasonal variation. The highest level in summer and the ecological risk should be considered based on the risk quotient values. These results demonstrated that the present DGT method is suitable for measuring, characterization, and risk assessment of BPs in freshwater and marine environment.

Effect of copper on bioconcentration of benzotriazole ultraviolet stabilizers (BUVSs) in common carp (Cyprinus carpio).

Benzotriazole ultraviolet stabilizers (BUVSs) have received increasing attention as emerging contaminants. However, most of the existing relevant studies focused on the adverse ecological effect of BUVSs under their single exposure, information about the bioconcentration potential of BUVSs and their joint exposure with heavy metals remains scarce. In this study, we investigated the bioconcentration kinetics of 6 frequently reported BUVSs in four main tissues of common carp under different Cu concentration. The bioconcentration factors (BCFs) and half-lives (t1/2) in the fish tissues ranged from 5.73 (UV-PS in kidney) to 1076 (UV-327 in liver), and 2.19 (UV-PS in kidney) to 31.5 (UV-320 in liver) days, respectively. Under the effect of Cu, an increase in BCF values was observed, which is mainly due to the decreased depuration rate (k2). These results indicated that BUVSs accumulated in fish and that Cu can affect the bioconcentration of BUVSs. This study provides important insight into the co-exposure of heavy metal and BUVSs, contributing to the perfection of BUVSs risk assessment.

Simultaneous evaluation of kinetic release of labile arsenic and phosphorus in agricultural soils using cerium oxide-based DGT.

The adsorption/desorption of arsenic (As) in agricultural soils is of utmost importance for the evaluation of its kinetic release and potential of entering the food chain by uptake of crops. However, the mobility of As in soils is closely related to the migration behavior of soil phosphorus (P) due to their chemical similarity. Here, the distribution and desorption kinetics of As and P in four different types of farmland soils were simultaneously estimated by cerium oxide-based diffusive gradients in thin films technique (CeO2-DGT) coupled with dynamic model of DGT induced fluxes in soils (DIFS). CeO2-DGT was deployed in the soils over 400 h to investigate the interactions between As and P for their migration behaviors. The accumulated masses of As in the DGT devices showed reverse orders with those of P among the four soils, indicating their competitive adsorption on soil solids. The distribution coefficients (Kdl) for the labile As and P derived from the DIFS model were mutually exclusive. Clay in the soil reduced the pool size of the labile As by increasing the irreversible adsorption of As on soil particles. The adsorption rate constants of As were much smaller than P but their desorption rate constants were comparable. Among the four soils, the soil with the highest soil labile As/P molar ratio measured by DGT showed the largest potential of As phytotoxicity. Both As and P could reach the equilibrium of resupply within 0.7- 18 min under DGT depletion, and significant negative correlation was observed between the desorption rate (kb) of As and clay content in the soils.

Characteristics and sources of environmentally persistent free radicals in PM2.5 in Dalian, Northeast China: correlation with polycyclic aromatic hydrocarbons.

Environmentally persistent free radicals (EPFRs) are an emerging class of environmental hazardous contaminants that extensively, stably exist in airborne particulate matter and pose harmful effects on human health. However, there was little research about the sources of EPFRs in actual atmospheric conditions. This study reported the occurrence, characteristics, and sources of EPFRs and polycyclic aromatic hydrocarbons (PAHs) in PM2.5 collected in Dalian, China. The concentrations of PM2.5-bound EPFRs ranged from 1.13 × 1013 to 8.97 × 1015 spins/m3 (mean value: 1.14 × 1015 spins/m3). Carbon-centered radicals and carbon-centered radicals with adjacent oxygen atoms were detected. The concentration of ∑PAHs ranged from 1.09 to 76.24 ng/m3, and PAHs with high molecular weight (HMW) were predominant species in PM2.5. Correlation of EPFRs with SO2, NO2, O3, and 12 kinds of PAHs indicated that both fuel (coal and biomass) combustion and photoreaction in atmosphere influenced the concentrations of EPFR. The positive matrix factorization (PMF) model results have shown that the primary sources contributed most of the EPFRs and those of secondary sources had a little proportion. Coal combustion (52.4%) was the primary contributor of EPFRs, followed by traffic emission (22.6%), industrial sources (9.6%), and secondary sources (9.2%) during the heating period, whereas industrial emission (39.2%) was the primary contributor, followed by coal combustion (38.1%), vehicular exhaust (23.5%), and secondary sources (9.6%) during the non-heating period. The finding of the present study provides an important evidence for further study on the formation mechanism of EPFRs in actual atmospheric to control the air pollution.

A review of environmental occurrence, analysis, bioaccumulation, and toxicity of organophosphate esters.

The ban and restriction of polychlorinated biphenyls (PCBs) and major brominated flame retardants (BFRs), including hexabromocyclododecane (HBCD) and polybrominated diphenyl ethers (PBDEs), due to their confirmed detrimental effects on wildlife and humans have paved the way for the wide application of organophosphate esters (OPEs). OPEs have been extensively used as alternative flame retardants, plasticizer, and antifoaming agents in various industrial and consumer products, which leads to an increase in production, usage, and discharge in the environment. We compile recent information on the production/usage and physicochemical properties of OPEs and discussed and compared the available sample treatment and analysis techniques of OPEs, including extraction, clean-up, and instrumental analysis. The occurrence of OPEs in sediment, aquatic biota, surface, and drinking water is documented. Toxicity, human exposure, and ecological risks of OPEs were summarized; toxicological data of several OPEs shows different adverse health effects on aquatic organisms and humans. Much attention was given to document evidence regarding the bioaccumulation and biomagnification potential of OPEs in aquatic organisms. Finally, identified research gaps and avenues for future studies are forwarded.

Relevance of macroinvertebrate communities as a water quality monitoring tool in ecosystems under harsh environmental conditions in the Rift Valley region.

Ecological assessment was performed in different thermal springs located in the Ethiopian Rift Valley area: Gergedi, Sodere, Halaba, and Gara. We assessed the habitat conditions, physicochemical characteristics, and macroinvertebrate composition at 12 sampling sites in four thermal spring systems. The physicochemical properties of the water samples varied among the sampling stations. Temperature ranged from 38.5 to 90°C among the 12 sites. Dissolved oxygen, which is essential to aquatic ecosystem normal functioning, was not detected at three sampling sites. An average of 109 macroinvertebrates were identified in three sampling campaigns. Relatively higher macroinvertebrate abundance 94 (86.2%) was registered in Gergedi than any other thermal spring sites. The macroinvertebrate abundance was 9 (8.3%) and 6 (5.5%) for the Gara and Sodere thermal springs. No macroinvertebrate communities were observed in all sites of Halaba thermal spring. From all macroinvertebrate groups, 82 (75.2%) were dipterans, 20 (18.4%) Oligochaeta, 5 (4.6%) Gastropoda, and the rest Hemipterans and Coleopterans, which comprises 2 (1.8%) individuals. Chironomidae was the dominant invertebrate taxa at all sites, and when the water temperature exceeds 42°C, it becomes the only taxon in the thermal springs. Macroinvertebrates were absent in thermal springs where the water temperature is 52°C or higher. Other diversity measures were not sensitive enough to discriminate sampling sites regardless of physicochemical variabilities except the richness and abundance. Water temperature, chloride, pH, and phosphate were identified as major determinants of macroinvertebrate richness in the Ethiopian Rift Valley region.

Tissue distribution and bioaccumulation of organophosphate esters in wild marine fish from Laizhou Bay, North China: Implications of human exposure via fish consumption.

Despite organophosphate esters (OPEs) are ubiquitous in the environment, limited information is available about their tissue-specific accumulation potential in marine fish and exposure risks. Ten fish species from the coastal area of Laizhou Bay, North China, were sampled and analyzed to investigate tissue levels, bioaccumulation, and human exposure risks of 20 OPEs. Seventeen OPEs were detected in fish tissues with total concentration ranging from 6.6-107 ng/g dry weight. The average log bioaccumulation factor (BAF) values of OPEs ranged from 2.8 to 4.4 in livers, 2.3-3.8 in muscles, 2.5-3.9 in gills, and 2.8-4.4 in kidneys. The log BAF values of OPEs significantly increased with increasing their log KOW values (r = 0.55-0.63, p < 0.001). The estimated daily intake of OPEs ranged from 1.7-12.0 and 3.1-22.1 ng/kg bw/d for rural and urban residents, respectively. The hazard quotients of OPEs were in the range of 4 × 10 -5 to 6.7 × 10 -4 and 7 × 10 -5 to 1.2 × 10 -3 for rural and urban residents, respectively. Results showed that the human health risks of OPEs associated with fish consumption is at low level.

Organophosphate esters (OPEs) in wetland soil and Suaeda salsa from intertidal Laizhou Bay, North China: Levels, distribution, and soil-plant transfer model.

Wetlands have attracted much attention due to releases of organophosphate esters (OPEs) and other emerging contaminants into this particular environment. Here, Suaeda salsa plants and wetland soils collected from Laizhou Bay, North China, were analyzed to investigate the levels, distribution, and soil-plant transfer of OPEs in these ecosystems. The Σ18OPEs concentrations ranged from 137 to 386 ng/g dry weight (dw), whereas in rhizosphere the concentrations were between 99.8 and 198 ng/g dw. Suaeda salsa rhizosphere could promote the absorption of OPEs in wetlands, and Suaeda salsa root presents a greater rate of absorption. The Σ18OPEs concentrations ranged from 32.9 to 56.8 ng/g dw in roots, 3.93 to 7.51 ng/g dw in stems, and 2.79 to 4.06 ng/g dw in leaves. Log RCFs, log TFr-s and log TFs-l showed no significant correlations with their log KOW, indicating the complexity of uptake and translocation in the natural environment. Predictive model for the OPEs availability to Suaeda salsa was established from the experimental data. The field-based BCFs of all OPEs were dependent on KOW, decreased with increasing KOW. This study provides important insights into the phytoremediation potential of OPEs using Suaeda salsa as an effective strategy and their role in environmental risk assessment of OPEs in wetlands.

Organophosphate esters in human serum in Bohai Bay, North China.

Organophosphate esters (OPEs), as a class of emerging flame retardant and plasticizers, have attracted particular attention due to their ubiquitous existence in the environment and potential effects on human health. Here, we investigated the levels of OPEs in human serum and examined the role of demographic variables on the body burden of such compounds. Of 11 OPEs screened, 8 were detected in human serum samples collected from a population (n = 89) in Bohai Bay, North China. The ∑OPE concentrations ranged from 4.7 to 948 ng/g lipid weight (lw), with a median concentration of 243 ng/g lw. Tris(2-chloroethyl)phosphate (TCEP) was identified as the most abundant OPEs with a median concentration of 214 ng/g lw. The concentrations of the triphenyl phosphate (TPhP) in older adults were higher than those in young adults (p < 0.05), and lower concentrations of tri-iso-butyl phosphate (TIBP) were observed in female samples compared to males. Furthermore, significant differences were observed in tri-n-propyl phosphate (TPrP) concentrations between urban and rural residence groups (p < 0.05). This study provides important information on the accumulation potential of OPEs in human bodies and suggests the need for further investigation to understand the potential human health risk.

Bioaccumulation and Trophic Transfer of Emerging Organophosphate Flame Retardants in the Marine Food Webs of Laizhou Bay, North China.

Despite the increase in production, usage, and discharge of organophosphate flame retardants (OPFRs), little information is available about their bioaccumulation and trophic transfer in the marine food web. In this study, seawater, sediment, and marine species (10 fish and 9 invertebrate species) collected from Laizhou Bay, North China, were analyzed to investigate the levels, bioaccumulation, and biomagnification of OPFRs in a marine food web. Of 20 OPFRs screened for, 17 were quantifiable in seawater, sediment, and organisms. The ∑OPFRs concentrations ranged from 0.2 to 28.4 ng/L in seawater, 0.1-96.9 ng/g dry weight in sediment, and 21.1-3510 ng/g lipid weight in organisms. Benthic fish accumulated more OPFRs than pelagic fish and invertebrates. A linear and significant increase of bioaccumulation factors with increasing lipophilicity of OPFRs was observed (R2 = 0.63, p < 0.05), and the biota-sediment accumulation factors increased with hydrophobicity up to log KOW = 4.59 and then decreased with increase in log KOW. Trophic magnification factors of OPFRs ranged from 1.06 to 2.52, indicating biomagnification potential of OPFRs in a marine food web. This study provides important insight into the biomagnification potential of OPFRs and suggests further investigation on this group of chemicals.

Uptake and depuration of eight fluoroquinolones (FQs) in common carp (Cyprinus carpio).

Fluoroquinolones (FQs) are extensively used in humans and animals, which have aroused wide attention due to the emergence of FQ resistant bacteria and frequent detection in water, sediment and organism. However, little information is available about the bioconcentration and tissue distribution of FQs in fish. In the present study, we investigated the uptake and depuration of eight FQs (balofloxacin (BAL), enoxacin (ENO), enrofloxacin (ENR), fleroxacin (FLE), lomefloxacin (LOM), moxifloxacin (MOX), ofloxacin (OFL), sparfloxacin (SPA)) in common carp under controlled laboratory conditions. The results showed that all target FQs could accumulate in fish tissues, and had a similar tendency over time during the whole uptake and depuration periods. The uptake rate constant (k1), depuration rate constant (k2) and half-lives (t1/2) were in the ranges of 0.007-3.599 L/(kg·d), 0.051-0.283 d-1 and 2.4-10.7 d, respectively. The ranges of bioconcentration factors (BCFs) were 0.24-39.55 L/kg, 0.21-24.97 L/kg and 0.04-1.07 L/kg in liver, kidney and muscle, respectively. BCFs of eight FQs decreased in the order: MOX > ENR > ENO ≈ BAL ≈ FLE ≈ OFL ≈ LOM ≈ SPA, which may be correlated with the substituents at positions 7 and 8 of the basic quinolone nucleus and the metabolic capacity. Besides, BCFs were relative with pH-adjusted distribution coefficient (log D), suggesting that molecular status of ionizable compounds strongly influenced the bioconcentration processes. The present study provides important insights for understanding the bioconcentration and tissues distribution of FQs.

Measurement and prediction of bioconcentration factors of organophosphate flame retardants in common carp (Cyprinus carpio).

The increase in the production and usage plus the toxicity nature of organophosphate flame retardants (OPFRs) has become a concern. However, limited information is available about the bioaccumulation potential of OPFRs in fish. In this study, we determined the 96 h LC50 s, and evaluated the bioaccumulation potential of six most frequently reported OPFRs in gill, kidney, liver, and muscle tissues of common carp (Cyprinus carpio) for 48 d, and a quantitative structure-activity relationship (QSAR) model was developed to predict bioconcentration factors (BCFs) for the remaining 16 OPFRs. The BCFs and half-lives (t1/2) in the tissues ranged from 6.54 (Tris (2-chloroisopropyl) phosphate, (TCPP)) to 528.15 (Tris (2-ethylhexyl) phosphate (TEHP)), and 2.25-5.78 days, respectively. The tissue-specific concentration and BCFs values followed the order of liver > kidney ≥ intestine >> muscle. The proposed QSAR model with a high cross-validated value (Q2(cum)) of 0.930 and a correlation coefficient of 0.94 was obtained and was able to predict log BCF from parameters related to molar volume and isotropic average static field polarizability. The results show that the model has a high level of accuracy, making the proposed approach a suitable method for predicting the log BCF.

Bioaccumulation and tissue distribution of antibiotics in wild marine fish from Laizhou Bay, North China.

Information about bioaccumulation and tissue distribution of antibiotics in wild marine fish is still limited. In the present study, tissue levels, bioaccumulation and distribution patterns of 9 sulfonamide (SA), trimethoprim (TMP), 5 fluoroquinolone (FQ), and 4 macrolide (ML) antibiotics were investigated in gill, muscle, kidney, and liver tissues of seven wild fish species collected from Laizhou Bay, North China in 2016. All the 19 antibiotics were detected in these fish tissues with the total concentrations ranging from 22ng/g dry weight (dw) to 500ng/g dw. The mean values of logarithm bioaccumulation factors (BAFs) in the gills, muscles, kidneys, and livers ranged from 2.2 to 4.8, 1.9 to 4.0, 2.5 to 4.9, and 2.5 to 5.4, respectively. Log BAFs of antibiotics in these tissues significantly increased (r=0.61-0.77, p<0.001) with their logarithm values of liposome-water distribution coefficient (Dlipw) except in the muscles, suggesting that Dlipw can well assess the bioaccumulation potentials of antibiotics in phospholipid-rich tissues. In general, the SAs, TMP, and FQs were primarily accumulated in the muscles and the MLs were primarily in the livers, which may be related to their toxicokinetic processes of these marine fish. The present study for the first time reported the tissue distribution patterns of antibiotics in wild marine fish.

Effect of copper on the accumulation and elimination kinetics of fluoroquinolones in the zebrafish (Danio rerio).

Fluoroquinolones (FQs) have attracted wide concerns due to their pseudo-persistent and universal presence in natural water. Here we exposed zebrafish separately to two FQs (enrofloxacin (ENR) and ofloxacin (OFL)) in different copper (Cu) concentrations for 20 days (d) in a flow-through system, followed by a 11 d depuration period in clean water to investigate compound specific bioaccumulation and tissue distribution. Two FQs could accumulate in zebrafish, and the high concentration was observed in liver. Moreover, the levels of FQs in different treatment groups were higher than the corresponding control fish group. The uptake rates (k1), elimination rates (k2), BCF value, and half-lives (t1/2) of FQs ranged from 0.02 to 3.28 d-1, 0.01 to 0.97 d-1, 0.33 to 109.33, 9.90 to 69.31 d, respectively. With Cu exposure concentration's increasing, k1 values in three tissues (liver, skin and gill) obviously decreased. The exposure concentration affected the BCF value significantly, but didn't change their relative compositions in liver, gill, skin, and muscle after long time exposure. BCF values of ENR were always a little bit higher than those of OFL in almost all the tissues (liver, skin and gill) in the low Cu concentration treatments, whereas, in the high Cu concentration treatments the bioconcentration factors (BCF) values of ENR were lower than the values of OFL. The exposure of Cu played an important role in the FQs bioconcentration and BCF. These results are meaningful for improved understanding and prediction of the behavior and fate of metallic and antibiotics in aqueous environments.