Combined effects of pH and dissolved organic matter on the availability of pharmaceuticals and personal care products in aqueous environment.

The interaction between pharmaceuticals and personal care products (PPCPs) with dissolved organic matter (DOM) can alter their bioavailability and toxicity. Nevertheless, little is known about how pH and DOM work together to affect the availability of PPCPs. This study investigated the impact of pH and DOM on the availability of seven PPCPs, namely Carbamazepine, Estrone, Bisphenol A, Testosterone Propionate, Triclocarban, 4-tert-Octylphenol and 4-n-Nonylphenol, using negligible depletion solid-phase microextraction (nd-SPME). The uptake kinetics of PPCPs by the nd-SPME fibers increased proportionally with DOM concentrations, likely due to enhanced diffusive conductivity in the unstirred water layer. At neutral pH, the partitioning coefficients of PPCPs for Humic Acid (log KDOC 3.87-5.25) were marginally higher than those for Fulvic Acid (log KDOC 3.64-5.11). Also, the log KDOC values correlated linearly with the log DOW (pH 7.0) values of PPCPs, indicating a predominant role for hydrophobic interactions in the binding of DOM and PPCPs. Additionally, specific interactions like hydrogen bonding, π-π, and electrostatic interactions occur for certain compounds, influenced by the polarity and spatial conformation of the compounds. For these ionizable PPCPs, the log DDOC values exhibit a strong dependence on pH due to the dual influence of pH on both DOM and PPCPs. The log DDOC values rose from pH 1.0 to 3.0, peaked at pH 5.0 to 9.0, and then (sharply) declined from 11.0 to 13.0. The reasons are that in strong acidic circumstances, the coiled and compressed shape of DOM inhibits the hydrophobic interaction, whereas in strong alkaline conditions, significant electrostatic repulsion reduces the sorption. This study reveals that the effects of DOM on the bioavailability of PPCPs are dependent on both pH and the specific compound involved.

Effects of carbamazepine on the central nervous system of zebrafish at human therapeutic plasma levels.

The fish plasma model (FPM) facilitated the environmental risk assessment of human drugs by using existing data on human therapeutic plasma concentrations (HTPCs) and predicted fish plasma concentrations (FPCs). However, studies on carbamazepine (CMZ) with both the mode of action (MOA) based biological effects at molecular level (such as neurotransmitter and gene level) and measured FPCs are lacking. Bioconcentration of CMZ in adult zebrafish demonstrated that the FPM underestimated the bioconcentration factors (BCFs) in plasma at environmental CMZ exposure concentrations (1-100 µg/L). CMZ significantly increased Glu and GABA, decreased ACh and AChE as well as inhibited the transcription levels of gabra1, grin1b, grin2b, gad1b, and abat when the actual FPCs were in the ranges of 1/1000 HTPC to HTPC. It is the first read-across study of CMZ integrating MOA-based biological effects at molecular level and FPCs. This study facilitates model performance against a range of different drug classes.

Effects of nanoplastics and microplastics on the availability of pharmaceuticals and personal care products in aqueous environment.

Nanoplastics (NPs) and microplastics (MPs) could act as potential carriers for pharmaceuticals and personal care products (PPCPs) and alter the bioavailability in the aquatic environment. The effects of NPs and MPs of polystyrene (PS) and polyethylene (PE) on the availability of five PPCPs including carbamazepine, bisphenol A, estrone, triclocarban and 4-tert-octylphenol were investigated by negligible depletion solid- phase microextraction (nd-SPME). The freely dissolved concentrations of PPCPs decreased with the increasing concentrations of NPs/MPs. The overall order of the sorption coefficients (logKNP / logKMP) of PPCPs was as follows: 100 nm PS > 50 nm PS > 1 µm PS > 100 µm PS > 100 µm PE. Sorption of PPCPs by NPs was generally 1-2 orders of magnitude stronger than to MPs. The log KNP / log KMP values (3.16-5.21) increased with the log KOW (2.45-5.28) of PPCPs, however, linear correlation was only observed between log KMP and log KOW. The particle size, specific surface area, aggregation state as well as hydrophobicity played an important role in the sorption. Coexistence of fulic acid (FA) with NPs inhibited the sorption due to the fouling of FA on NPs. This study suggests that sorption of PPCPs to MPs/NPs could reduce bioavailability of PPCPs in the aquatic environment.

Encapsulating gold nanoclusters into metal-organic frameworks to boost luminescence for sensitive detection of copper ions and organophosphorus pesticides.

Gold nanoclusters (Au NCs) with luminescence property are emerging as promising candidates in fluorescent methods for monitoring contaminants, but low luminescence efficiency hampers their extensive applications. Herein, GSH-Au NCs@ZIF-8 was designed by encapsulating GSH-Au NCs with AIE effect into metal-organic frameworks, achieving high luminescence efficiency and good stability through the confinement effect of ZIF-8. Accordingly, a fluorescent sensing platform was constructed for the sensitive detection of copper ions (Cu2+) and organophosphorus pesticides (OPs). Firstly, the as-prepared GSH-Au NCs@ZIF-8 could strongly accumulate Cu2+ due to the adsorption property of MOFs, accompanied by a significant fluorescence quenching effect with a low detection limit of 0.016 µM for Cu2+. Besides, thiocholine (Tch), the hydrolysis product of acetylthiocholine (ATch) by acetylcholinesterase (AchE), could coordinate with Cu2+ by sulfhydryl groups (-SH), leading to a significant fluorescence recovery, which was further used for the quantification of OPs owing to its inhibition to AChE activity. Furthermore, a hydrogel sensor was explored to accomplish equipment-free, visual, and quantitative monitoring of Cu2+ and OPs by a smartphone sensing platform. Overall, this work provides an effective and universal strategy for enhancing the luminescence efficiency and stability of Au NCs, which would greatly promote their applications in contaminants monitoring.

Copper Peroxide Nanodots Encapsulated in a Metal-Organic Framework for Self-Supplying Hydrogen Peroxide and Signal Amplification of the Dual-Mode Immunoassay.

The necessary step of directly adding hydrogen peroxide (H2O2) into the detection system in traditional immunoassays hampers their applications as a portable device for point-of-care analysis due to the unstable liquid form of H2O2. Herein, a strategy of self-supplying H2O2 and signal amplification triggering by copper peroxide nanodots encapsulated (CPNs) in metal-organic frameworks (ZIF-8) was proposed in an immunoassay for dual-signal detection of bisphenol A (a typical emerging organic pollutant), which was further fabricated as a lab-in-a-tube device integrated with a smartphone sensing platform. Herein, CPNs@ZIF-8 was modified on the antibody against bisphenol A; after the competitive binding of analytes, coating antigens, and antibodies, the released H2O2 and Cu2+ from encapsulated CPNs under the acidic condition will trigger a Fenton-like reaction to generate ·OH for oxidization of TMB; meanwhile, Cu2+ could quench the fluorescence of GSH-Au NCs, resulting in dual-mode signals for measurements. Most importantly, self-supplying H2O2 with high stability was undertaken by CPNs, and the remarkably increased signal molecule (CPN) loading was ascribed to the excellent capacity of metal-organic frameworks (ZIF-8). In addition, good recoveries were obtained from a colorimetric/fluorescent dual-mode strategy. The constructed device demonstrated great potential as a universal platform for rapid detection of various environmental contaminants using corresponding antibodies relying on its performance of satisfactory stability, sensitivity, and accuracy.

Self-powered aptasensor for picomole level pollutants based on a novel enzyme-free photofuel cell.

Atrazine (ATZ) is a highly toxic chlorine-containing aromatic structural triazine endocrine disruptor. Due to its chemical stability and electrochemical inertness, it is of great challenge and significance to establish a simple, portable, and in situ electrochemical sensor for ATZ. In the present work, a self-powered aptasensor (SPA) based on a novel enzyme-free photofuel cell (PFC) is successfully developed for ATZ for the first time. The designed SPA is constructed by the Ti-Fe-O nanotubes/nickel hydroxide (Ti-Fe-O NTs/Ni(OH)2) photoanode and Au/aptamer (Au/Apt) cathode, responsible for the spontaneous generation of electrons and specific recognition of ATZ, respectively. It is worth noting that Ti-Fe-O NTs on the photoanode can exhibit good visible-light absorption property, and modified Ni(OH)2 further enhances the photo-generated carrier separation and improves the output power generation of the SPA. The recognition is set at the cathode to ensure the detection of ATZ and the anti-interference ability. Under the separation mode, the constructed SPA has a high output power (390 µW cm-2), much better than most previous reports. It can further show specific recognition of ATZ with prominent sensitivity and a limit of detection (LOD) as low as 5.4 pM. Moreover, it has been applied to the real water sample analysis with satisfactory results. A promising self-powered sensing platform based on an enzyme-free PFC has therefore been provided for picomole level pollutants with high sensitivity and outstanding selectivity.

Simultaneous determination of 31 endocrine disrupting chemicals in fish plasma by solid-phase extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry.

Solid phase extraction combined with ultra-performance liquid chromatography-tandem mass spectrometry was developed for the simultaneous determination of 31 endocrine-disrupting chemicals in fish plasma. The strong anion exchange/primary-secondary amine cartridge and the mixed cation exchange cartridge were used in tandem instead of using a single mixed cation exchange cartridge for sample purification. Suitable eluents were selected for each of the two cartridges: 4.5% ammonia/acetonitrile solution for cartridges in tandem and acetone:n-hexane (V:V = 3:7) for the strong anion exchange/primary-secondary amine cartridge alone. With this optimized Solid phase extraction method, the recoveries of 31 endocrine disrupting chemicals were between 43.0% and 131.3%, the method detection limits were 0.45 to 1.35 ng/ml, and the limits of quantitation were 1.50-4.50 ng/ml. The innovative pretreatment method that connects two cartridges in tandem is well positioned to mitigate the matrix effects of fish plasma, thereby improving the accuracy of multiclass endocrine-disrupting chemicals determination. The significance of this method is to facilitate the application of the fish plasma model for the environmental risk assessment of endocrine-disrupting chemicals.

A Lab-in-a-Syringe Device Integrated with a Smartphone Platform: Colorimetric and Fluorescent Dual-Mode Signals for On-Site Detection of Organophosphorus Pesticides.

Herein, a portable lab-in-a-syringe device integrated with a smartphone sensing platform was designed for rapid, visual quantitative determination of organophosphorus pesticides (OPs) via colorimetric and fluorescent signals. The device was chiefly made up of a conjugate pad labeled with cetyltrimethylammonium bromide-coated gold nanoparticles (CTAB-Au NPs) and a sensing pad modified by ratiometric probes (red-emission quantum dots@SiO2 nanoparticles@green-emission quantum dots, rQDs@SiO2@gQDs probe), which was assembled through a disposable syringe and reusable plastic filter. In the detection system, thiocholine (Tch), the hydrolysis product of thioacetylcholine (ATch) by acetylcholinesterase (AchE), could trigger the aggregation of CTAB-Au NPs, resulting in a significant color change from red to purple. Then, CTAB-Au NPs flowed vertically upward and bound to the rQDs@SiO2@gQDs probe on the sensing pad, reducing the fluorescence resonance energy transfer effect between CTAB-Au NPs and gQDs. Meanwhile, rQDs embedded in SiO2 NPs remained stable as internal reference fluorescence, achieving a color transition from red to green. Thus, based on the inhibition of AChE activity by OPs, a colorimetric and fluorescent dual-mode platform was constructed for on-site detection of OPs. Using glyphosate as a model, with the support of a color recognizer application (APP) on a smartphone, the ratio of red and green channel values could be utilized for accurate OP quantitative analysis ranging from 0 to 10 µM with a detection limit of 2.81 nM (recoveries, 90.8-122.4%; CV, 1.2-3.4%). Overall, the portable lab-in-a-syringe device based on a smartphone sensing platform integrated sample monitoring and result analysis in the field, implying great potential for on-site detection of OPs.

Bioaccessibility evaluation of pharmaceuticals in market fish with in vitro simulated digestion.

The consumption of pharmaceuticals-contaminated aquatic products could pose risks to human health, and risk assessments considering bioaccessibility can provide better dietary recommendations. In this study, the bioaccessibility of 6 pharmaceuticals (sulfadiazine (SD), sulfapyridine (SPD), roxithromycin (ROX), tylosin (TYL), diclofenac (DIC) and carbamazepine (CMZP)) in several fish species collected from Shanghai markets was evaluated using in vitro simulated digestion. The total mixed pharmaceuticals concentration in freshwater fish were lower than those in marine fish, and statistics showed that the total concentrations of SD, SPD and CMZP in freshwater fish were significantly lower than those of marine fish (p < 0.05). The bioaccessible concentration of each pharmaceutical accounted for 26.3% (TYL) to 101.5% (CMZP) of the total concentration in market fish (n = 70). The bioaccessibility of 6 pharmaceuticals in species of fish was 18.8% (cutlassfish) to 99.6% (bream), which may be related to the physical-chemical properties of the pharmaceutical and the characteristics of the matrix (e.g. lipid content). According to health risk assessments, the consumption of market fish in Shanghai posed no remarkable risk to human health (hazard quotient < 0.099). Ignoring the bioaccessibility of pharmaceuticals in aquatic products might overestimate the human health risks by dietary exposure.

Oxidized nanoscale zero-valent iron changed the bioaccumulation and distribution of chromium in zebrafish.

Influences of colloidal stabilities of nanoparticles (NPs) on the bioaccumulation of co-existing pollutants remains largely unknown. In this study, two oxidation products of nanoscale zero-valent iron (nZVI) with totally varied colloidal stabilities, termed highly oxidized nZVI (HO-nZVI) and lowly oxidized nZVI (LO-nZVI), were exposed to zebrafish with chromium (Cr); this approach was used to investigate the impacts of colloidal stability of oxidized nZVI on the bioaccumulation of Cr in zebrafish. A significant increase in the Cr and NP content in the viscera of fish in the presence of the oxidized nZVI after 20 days of exposure was confirmed, which indicated that Cr was consumed by fish through the uptake of the NPs. Furthermore, a significantly higher level of the HO-nZVI accumulated in the viscera in contrast to LO-nZVI, which suggested that the colloidal stability of NP is a crucial factor when evaluating the accessibility of NPs to zebrafish. Thus, HO-nZVI induced a significantly stronger enhancement of Cr content in fish than LO-nZVI. Our results suggest that oxidized nZVI will act as the carrier of co-existing heavy metals and change the transportation and distribution of heavy metals in zebrafish; moreover, the colloidal stability of NP will have a significant influence on the bioaccumulation of coexisting Cr.

A novel signal amplification strategy based on the competitive reaction between 2D Cu-TCPP(Fe) and polyethyleneimine (PEI) in the application of an enzyme-free and ultrasensitive electrochemical immunosensor for sulfonamide detection.

Nanozymes with peroxidase-like activity have been widely used as signal labels in electrochemical immunosensors. However, these sensors always suffer from some shortcomings during the processes underlying nanozyme labeling, including complex reactions, nanozyme inactivation after being decorated on the antibodies. To solve these problems, a novel electrochemical immunosensor was designed for ultrasensitive detection of sulfonamides (SAs), in which the synthesized 2D Cu-TCPP(Fe) with peroxidase-like property was used as a nanozyme that was directly modified on the electrode surface. Meanwhile, the structure of 2D Cu-TCPP(Fe) could be destroyed by the polyethyleneimine (PEI) from PEI-GO@Ab2 due to the stronger affinity between PEI and Cu2+, leading to an activity change of the prepared nanozyme. When H2O2 was introduced to the system, the electrochemical current was significantly declined owing to the peroxidase activity of 2D Cu-TCPP(Fe) decreased, which led to signal amplifications. Under the optimized conditions, this strategy had a wide detection range (1.186-28.051 ng/mL), satisfactory accuracy and precision (recoveries, 64-118%; CV, 2.16-7.27%) with a low detection limit of 0.395 ng/mL. The findings of this study indicate that the electrochemical immunosensor we developed has great potential and can be used for enzyme-free detection of SAs in environmental samples.

Evaluating the effect of different modified microplastics on the availability of polycyclic aromatic hydrocarbons.

Microplastics (MPs) discharged into the natural environment undergo various wearthering pathways, such as mechanical abrasion and ultraviolet (UV) irradiation. However, little is known about the effects of such aged MPs on the bioavailability of hydrophobic organic compounds (HOCs) in aqueous environments. To simulate the natural oxidation and UV-ageing process of MPs, three kinds of modified polyethylene MPs were obtained by plastic etching processes common in industry and UV irradiation, namely, etched MPs (EMPs), UV-aged MPs (UV-MPs), and etched MPs followed by UV ageing (UV-EMPs). The modified MPs showed a higher content of surface oxygen-containing groups than the pristine MPs, and the specific surface area and pore volume increased significantly after etching and ultraviolet ageing, especially for the EMPs (1.67 m2 g-1 and 0.0049 cm³ g-1) and UV-EMPs (2.37 m2 g-1 and 0.0089 cm³ g-1). The effect of modified MPs on the availability of 10 polycyclic aromatic hydrocarbons (PAHs, logKow 4.18-6.20) was evaluated by negligible-depletion solid-phase microextraction (nd-SPME). The free concentrations (Cfree) of most PAHs (except for less hydrophobic PAHs, logKow 4.18 and 4.56) decreased with an increasing concentration of MPs. The logarithms of the sorption coefficients of PAHs with various MPs (logKMPs, logKUV-MPs, logKEMPs and logKUV-EMPs) were linearly correlated with logKow, suggesting that the sorption is hydrophobicity dependent. Compared with the results for pristine MPs (logKMP 3.80-4.95), UV ageing only slightly enhanced the sorption of PAHs by MPs (logKUV-MPs 3.71-4.98), whereas the plastic etching processes significantly enhanced sorption (logKEMPs 3.85-5.18 and logKUV-EMPs 3.90-5.28). The sorption of PAHs to MPs is mainly based on partitioning; however, a mechanism of adsorption also likely takes place in EMPs and UV-EMPs due to hydrogen bonding and π-π interactions. Desorption study indicated that PAH desorption from MPs are dominated by film diffusion. However, intraparticle diffusion also takes great part for the EMPs. These results suggest that modification of MPs in the natural environment will change the availability of HOCs.

Electrochemical immunosensor based on Ag+-dependent CTAB-AuNPs for ultrasensitive detection of sulfamethazine.

An electrochemical biosensor was proposed utilizing an improved amplification strategy for the rapid detection of sulfamethazine (as a model target) in aquatic environments. In this competitive immunoassay, cetyltrimethylammonium bromide-capped gold nanoparticles (CTAB-AuNPs) were used as a signal amplifier and electrode matrix and coated with an antigen-antibody (Cag-Ab1) specific binding system as a recognition unit for the target compound. In addition, silver nanoparticle labels were functionalized with dendritic fibrous nanosilica (DFNS@AgNPs) and decorated onto chitosan/single walled carbon nanohorn (CS/SWCNH)-modified glass carbon electrodes (GCEs), which improved the electron transfer rate and increased the surface area, enabling more coating antigens to be captured. Under acidic conditions, massive amounts of the Ag+ bound to the surface of the AuNPs dissolved, and consequently, formed Ag+@CTAB-AuNP complexes, which resulted in a distinctly improved peroxidase-like activity and enhanced current response. Furthermore, the destroyed Ab1-Ab2-DFNS conjugation greatly decreased the impedance, bringing about the amplification of the electrochemical signals. After optimization of the parameters, the proposed approach exhibited excellent performance, including good sensitivity (LOD, 0.0655 ng/mL) and satisfactory accuracy (recoveries, 79.02%-118.39%; CV, 3.18%-9.82%), which indicates the great potential of this strategy for the rapid detection of trace pollutants in the environments.

Correction to: Occurrence of 25 pharmaceuticals in Taihu Lake and their removal from two urban drinking water treatment plants and a constructed wetland.

The article Occurrence of 25 pharmaceuticals in Taihu Lake and their removal from two urban drinking water treatment plants and a constructed wetland, written by Xia-Lin Hu, Yi-Fan Bao, Jun-Jian Hu, You-Yu Liu and Da-Qiang Yin, was originally published electronically on the publisher's internet portal.

Electrochemical Biosensor Based on Tetrahedral DNA Nanostructures and G-Quadruplex-Hemin Conformation for the Ultrasensitive Detection of MicroRNA-21 in Serum.

MicroRNAs (miRNAs) play important roles as significant biomarkers in disease diagnostics. Here, an electrochemical biosensor was developed for the quick, sensitive, and specific detection of miRNAs from human-serum samples using three-dimensional (3D) DNA tetrahedron-structured probes (TSPs) and duplex-specific nuclease (DSN). The designed TSPs were composed of a recognition sequence that corresponded to a target miRNA and a G-quadruplex sequence that was combined with hemin to mimic the biocatalytic functions for H2O2 reduction and l-cysteine oxidation. After hybridization with miRNA, the TSPs were immobilized on the Au electrode to shape the DNA-RNA double strands, which could be discriminated by DSN for hydrolysis of the DNA in the heteroduplexes to generate significant change in the reduction currents. Under optimal conditions, the biosensor showed a wide linear response ranging from 0.1 fM to 0.1 pM, with a low detection limit of 0.04 fM. Meanwhile, the method showed acceptable accuracy and precision for the determination of miRNAs in serum after a series of assessments.

A novel fluorescence immunoassay based on AgNCs and ALP for ultrasensitive detection of sulfamethazine (SMZ) in environmental and biological samples.

A novel indirect competitive fluorescence immunoassay based on the quenching of I- to silver clusters (AgNCs) was developed for the highly selective and ultrasensitive detection of sulfamethazine (SMZ). In this system, alkaline phosphatase (ALP) was labeled on the secondary antibody (Ab2). And after a competition step, magnesium ascorbyl phosphate could be catalyzed to produce ascorbic acid under the catalysis of ALP. Subsequently, I2 was introduced and further reduced to I- in the presence of ascorbic acid, triggering the fluorescence quenching of AgNCs dispersed in isopropanol (IPA) buffer. More importantly, trace I- could lead to an obvious reduction in fluorescence signal, indicating the sensitivity of this method would be greatly improved. Under the optimal condition, this improved method for the SMZ detection has a lower detection of limit (LOD, 0.05000 µg/L) with a wider range (0.1400-71.71 µg/L). After an evaluation, the fluorescence ELISA proposed in this work has satisfactory accuracy and reliability (recoveries, 84.18-118.6%; CV, 2.03-7.64%), illustrating good performance and great potential for the detection of trace SMZ in environmental and biological samples.

Simultaneous determination of 29 pharmaceuticals in fish muscle and plasma by ultrasonic extraction followed by SPE-UHPLC-MS/MS.

A confirmatory method for the simultaneous detection of 29 pharmaceuticals in fish muscle and plasma was developed by using solid-phase extraction combined with ultra-high performance liquid chromatography and tandem mass spectrometry. Fish samples were extracted with methanol and enriched using Oasis HLB solid-phase extraction columns in one step. Twenty-nine target pharmaceuticals were quantified by the internal standard method and the calibration curves showed good linearity in a wide range with determination coefficients of greater than 0.913. The detection limits of the pharmaceuticals ranged from 0.01 to 2.00 µg/kg (µg/L). The applicability of the method was checked by precision and recovery experiments. The average recoveries of the 29 pharmaceuticals were between 61 and 111%, and all the relative standard deviations were below 25%. Our reported method has been demonstrated to be sensitive, convenient, rapid, and reliable for the simultaneous determination of 29 pharmaceuticals in fish muscle and plasma. Real sample determination showed that 25 and 9 of the 29 compounds were detected in fish muscle and plasma, respectively.

Nanomaterials Safer-by-Design: An Environmental Safety Perspective.

Designing safer nanomaterials and nanostructures has gained increasing attention in the field of nanoscience and technology in recent years. Based on the body of experimental evidence contributed by environmental health and safety studies, materials scientists now have a better grasp on the relationships between the nanomaterials' physicochemical characteristics and their hazard/safety profiles. Therefore, it is expected that an integration of design synthesis and safety assessment will foster nanomaterials safer-by-design by considering both applications and implications. From the environmental safety perspective, the most recent advances that demonstrate effective nanomaterials safer-by-design are highlighted.

Bioaccumulation, distribution and elimination of lindane in Eisenia foetida: The aging effect.

Soil aging will influence the chemical speciation of pesticides, thus affecting the uptake route to be bioavailable to the organism. So far, studies on the possible effects of the uptake route on the distribution and elimination of pesticides in the organism that also considers effects of aging are limited. In our study, Eisenia fetida was exposed to 4.5 mg kg-1 lindane aging for 0, 30 and 180 d, and the accumulation, distribution and elimination of lindane in the earthworms were analyzed. The results showed that the 6 h Tenax-extracted fraction exhibited a good linear correlation with the lindane accumulated in the earthworms. With aging time increasing, the bioaccumulation of lindane decreased and the accumulative balance was more easily reached in the earthworms. Lindane distributions were found in the whole earthworm and the proportions of lindane content at sub-organism level and the mass distribution of each fraction were similar for 0 d and 180 d aged groups. The foregut accumulated the highest content of lindane (20%) relative to its low mass distribution proportion (10%). The elimination rate of lindane in the earthworms decreased with aging time extending. Our conclusion was that the 6 h Tenax extraction could be used to assess the bioavailability of aging lindane. Although soil aging decreased the bioavailability of lindane, the soil-bound lindane entered the earthworm through dietary route would take longer to depurate from the organisms than free lindane, which implied the potential ecological risk of bound pesticide residues.

Distribution and relevance of iodinated X-ray contrast media and iodinated trihalomethanes in an aquatic environment.

Distribution and relevance of iodinated X-ray contrast media (ICM) and iodinated disinfection byproducts (I-DBPs) in a real aquatic environment have been rarely documented. In this paper, some ICM were proven to be strongly correlated with I-DBPs through investigation of five ICM and five iodinated trihalomethanes (I-THMs) in surface water and two drinking water treatment plants (DWTPs) of the Yangtze River Delta, China. The total ICM concentrations in Taihu Lake and the Huangpu River ranged from 88.7 to 131 ng L-1 and 102-252 ng L-1, respectively. While the total I-THM concentrations ranged from 128 to 967 ng L-1 in Taihu Lake and 267-680 ng L-1 in the Huangpu River. Iohexol, the dominant ICM, showed significant positive correlation (p < 0.01) with CHClI2 in Taihu Lake. Iopamidol and iomeprol correlated positively (p < 0.01) with some I-THMs in the Huangpu River. The observed pronounced correlations between ICM and I-THMs indicated that ICM play an important role in the formation of I-THMs in a real aquatic environment. Characteristics of the I-THM species distributions indicated that I-THMs may be transformed by natural conditions. Both DWTPs showed negligible removal efficiencies for total ICM (<20%). Strikingly high concentrations of total I-THMs were observed in the finished water (2848 ng L-1 in conventional DWTP and 356 ng L-1 in advanced DWTP). Obvious transformation of ICM to I-THMs was observed during the chlorination and ozonization processes in DWTPs. We suggest that ICM is an important source for I-DBP formation in the real aquatic environment.