Occurrence and Health Risks of Organic Micropollutants in Tap Water in Dalian.

Organic micropollutants (OMPs) in tap water may pose risks to human health. Previous studies on the potential health risks of OMPs in tap water may have underestimated the potential health risks of OMPs due to their limited coverage in target pollutants and incomplete toxicity data. In this study, tap water samples were collected in 37 sampling sites in Dalian, China. More than 1,200 target pollutants were screened by combining screening analysis and target analysis. A total of 93 OMPs were detected, with concentration summation ranging from 157 to 1.7 × 104 ng/L among different sampling sites. A total of 17 OMPs (12 agrochemicals, 3 pharmaceuticals and personal care products, and 2 other compounds) were detected in over 80% of the sampling sites. Especially, imidacloprid, tebuconazole, and atrazine-desethyl were found in all the sampling sites. Computational toxicology models were adopted to predict the missing toxicity threshold values of the identified chemicals. Noncarcinogenic risks were estimated to be negligible among all the sampling sites, while carcinogenic risks at six sites were above 10-6 but below 10-4, indicating non-negligible risks. Griseofulvin contributed the most to the carcinogenic risk. This study offers valuable insights that can guide future initiatives to safeguard tap water safety.

An overview of organic contaminants in indoor dust, their health impact, geographical distribution and recent extraction/analysis methods.

People spend a substantial proportion of their time indoors; therefore, exposure to contaminants in indoor dust is persistent and profuse. According to the findings of recent studies, contaminants such as flame retardants (FRs), organochlorines (OCs), and phthalate esters (PAEs) are more prevalent in indoor dust. The discrepancy in the geographical distribution of these chemicals indicates country-specific applications. However, many studies have revealed that chlorophosphates, polychlorinated biphenyls (PCBs) and di-2-ethylhexyl phthalate are frequently detected in indoor dust throughout the world. Although some chemicals (e.g., OCs) were banned/severely restricted decades ago, they have still been detected in indoor dust. These organic contaminants have shown clear evidence of carcinogenic, neurotoxic, immunogenic, and estrogenic activities. Recent extraction methods have shown their advantages, such as high recoveries, less solvent consumption, less extraction time and simplicity of use. The latest separation techniques such as two-dimensional gas/liquid chromatography, latest ionization techniques (e.g., matrix-assisted laser desorption/ionization (MALDI)), and modern techniques of mass spectrometry (e.g., tandem mass spectrometry (MS/MS), time-of-flight (TOF) and high-resolution mass spectrometry (HRMS)) improve the detection limits, accuracy, reproducibility and simultaneous detection of organic contaminants. For future perspectives, it is suggested that the importance of the study of dust morphology for comprehensive risk analysis, introducing standard reference materials to strengthen the analytical methods, adopt common guidelines for comparison of research findings and the importance of dust analysis in the developing world since lack of records on the production and usage of hazardous substances. Such measures will help to evaluate the effectiveness of prevailing legislations and to set up new regulations.

Comprehensive Target Analysis for 484 Organic Micropollutants in Environmental Waters by the Combination of Tandem Solid-Phase Extraction and Quadrupole Time-of-Flight Mass Spectrometry with Sequential Window Acquisition of All Theoretical Fragment-Ion Spectra Acquisition.

There are many thousands of chemicals in use for a wide range of purposes, and highly efficient analytical methods are required to monitor them for protection of the environment. In order to cope with this difficult task we developed a novel, comprehensive method for 484 substances in water samples. In this method target chemicals were extracted by tandem SPE and then determined by LC-QTOF-MS-SWATH. Targets were unambiguously identified using retention times, accurate masses of a precursor and two product ions, their ion ratios, and accurate MS/MS spectrum. Quantitation was achieved by the internal standard method using a precursor ion. Results of recovery tests at two concentrations (50 and 500 ng L-1) showed average recoveries of 87.5% and 87.0% (RSD, 9.1% and 9.4%), respectively. Limits of detection of one-half of the targets were below 1.0 ng L-1. The method was applied to the influent and effluent of a sewage treatment plant, and around 100 chemicals were detected. Results of examination on matrix effects using their extracts spiked with 209 pesticides showed that the ratios of detected amounts between the extracts and the standard solution were 89.8% (influent) and 91.7% (effluent), respectively. In addition, investigation on the stability of calibration curves by injecting the same standards for 1 year showed that their quantitative results did not change; average accuracy was 103.3% (RSD, 10.0%), indicating that the calibration curves can be used for an extended period of time without calibration, and quantitative retrospective analysis can be done after creating calibration curves for new targets.

Quorum sensing between Gram-negative bacteria responsible for methane production in a complex waste sewage sludge consortium.

Quorum sensing (QS) plays a key role in activating bacterial functions through small molecules called autoinducers. In this study, the QS of Gram-negative bacteria in waste sewage sludge (WSS) was downregulated by adding the quorum quenching enzyme, AiiM lactonase, which cleaved the acyl-homoserine lactone (AHL) autoinducer signals from Gram-negative bacteria, and subsequently methane production was inhibited by over 400%. The pH was lowered after 2 days in the anaerobic fermentation whereas protease activity at the hydrolysis step was almost the same with or without AiiM. The production of acetic acid significantly increased during the fermentation in the presence of AiiM. The bacterial community at day 2 indicated that the population of Gram-positive bacteria increased in the presence of AiiM, and the percentage of Gram-negative bacteria decreased in the WSS containing AiiM. The change in the bacterial community in the presence of AiiM may be due to the different antimicrobial agents produced in the WSS because some of the Gram-positive bacteria were killed by adding the solid-phase extraction (SPE) fraction from the WSS without AiiM. In contrast, the SPE fraction with AiiM had reduced bactericidal activity against Gram-negative bacteria. Thus, bacterial signaling between Gram-negative bacteria is critical for methane production by the microbial consortia.

Survey on the micro-pollutants presence in surface water system of northern Serbia and environmental and health risk assessment.

This study demonstrates the occurrence of 940 organic micro-pollutants in surface water of four rivers, one irrigation canal system, and two lakes in Vojvodina Province, the northern part of Serbia, summing in total eighteen samples. The number of detected chemicals ranged from 22 to 84, with 127 micro-pollutants detected at least once, representing 13% of the studied substances. The targeted compounds include n-alkanes, sterols, polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides polychlorinated biphenyls, pesticides, pharmaceutical active compounds, industrial chemicals, plasticizers, etc. Among the analysed compounds, sterols were the most dominant with maximum quantified concentrations. The substances which were quantified with frequency over 50% were two PAHs (2-methylnaphthalene, benzo(ghi)perylene), five sterols (cholesterol, cholestanol, stigmasterol, fucosterol, beta-sitosterol), three pharmaceuticals and personal care products (L-menthol, diethyltoluamide, caffeine), and ten household chemicals (4-tert-octylphenol, dimethyl phthalate, methyl palmitate, phenylethyl alcohol, 1-nonanol, alpha-terpineol, 2-phenoxy-ethanol, methyl myristate, acetophenone, and 2-ethyl-1-hexanol). The list of priority substances under the European Union Directive 2013/39/EU includes 49 priority substances (PSs) out of which 34 were analysed. Among these, eleven PSs were quantified, and only two compounds (fluoranthene and benzo (a) pyrene) exceeded EU Environmental Quality Standards targeted values. The obtained results were compared with the previously published data that dealt with the same targeted number of micro-pollutants in sediment samples. This revealed connections between the same sampling locations. Environmental risk assessment showed the existence of potential ecological risk as 72% of the obtained values for the ecological hazard index (HI) at investigated locations were higher that the targeted value (HI > 1). Estimated values for hazard quotient (HQ) and hazard index (HI) for non-carcinogenic risk were lower than the targeted value, indicating no non-carcinogenic risk through dermal contact and non-intentional ingestion of water. Estimated values for cancer risk were all below 1 × 10-6, which is not considered to pose significant human health risk.

Contaminants in Liquid Organic Fertilizers Used for Agriculture in Japan.

To provide an overview of anthropogenic contaminants in liquid organic fertilizers (LOFs), products from four biogas plants in Kyushu, Japan, were analyzed for a wide range of contaminants, including copper, cadmium, tributyltin (TBT), dibutyltin (DBT), perfluorooctane sulfonate, 952 semi-volatile organic compounds, and 89 antibiotics. The highest concentrations of copper (31.1 mg/L) and cadmium (0.08 mg/L) were found in LOFs from the Hita biogas plant. Only ofloxacin and sulfapyridine were detected in total 89 antibiotics screened. TBT, DBT, and perfluorooctane sulfonate were present at low concentrations in the LOFs from all four locations. Among the 952 semi-volatile organic compounds, 78 compounds were detected in at least one sample and were present at concentrations between 1.2 and 139.6 mg/L. On the basis of comparisons with previous studies and quality standards for the use of organic fertilizers, the concentrations of contaminants in the studied LOFs indicate that they might be safe for agricultural purposes.

Joint probabilistic risk of organic micropollutants in the aquaculture seawater around Liaodong Peninsula.

The limited number of organic micropollutants (OMPs) investigated in aquaculture seawater may underestimate the risk to marine organisms. It is critical to comprehensively investigate the occurrence of diverse OMPs in mariculture area and assess their joint risks to coastal marine organisms. Herein, the joint risks caused by multiple substances were assessed based on the screened results of approximately 1300 non-polar to polar OMPs in the seawater of mariculture ponds and raft culture areas around Liaodong Peninsula. In this study, 48 out of 886 non-polar to low-polar OMPs were detected at least once in 36 seawater samples, including 16 alkanes, 6 phthalate esters, 6 pesticides, 5 polycyclic aromatic hydrocarbons, etc. For 99 detected OMPs from both this study and our previously reported study, their aquatic toxicity data were comprehensively collected to assess the probabilistic risk. For 14 OMPs with sufficient toxicity data, their species sensitivity distribution curves were established. The results show that only three pollutants - ametryn, atrazine and diuron - alone adversely affect >5 % of coastal marine organisms. However, for the joint risks, up to 15.2 % of coastal marine organisms were affected by 14 OMPs under long-term exposure, suggesting that the OMP mixtures could enhance adverse effects. Although the ecological risks for most of compounds were acceptable, the joint risks of co-pollution by various OMPs cannot be ignored. The findings could support risk management of pollutants in aquaculture seawater, thereby contributing to the conservation of coastal marine biodiversity.

Sediment contamination with polybrominated diphenyl ethers and alternative brominated flame retardants: case study in urban lakes of Hanoi, Vietnam.

Information regarding the contamination of brominated flame retardants (BFRs) in lake sediments from Vietnam and Southeast Asia is still very limited. To fill such knowledge gaps, surface sediment samples from five urban lakes in Hanoi, Vietnam, were analyzed for polybrominated diphenyl ethers (PBDEs) and some other BFRs. Concentrations of total PBDEs ranged from 1.1 to 26 (median 6.6) ng/g dry weight with the most predominant congeners as BDE-209 (62 ± 17%), BDE-99 (10 ± 8%), and BDE-47 (6 ± 5%). Concentrations of other BFRs decreased in the order: decabromodiphenyl ethane (DBDPE) > 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) > hexabromobiphenyl (BB-153) > pentabromoethylbenzene (PBEB), which were about one to two orders of magnitude lower than PBDEs. BDE-209 and DBDPE were highly correlated (Pearson's r = 0.879; p < 0.01), suggesting their similar applications and/or environmental fate. Potential sources of BFRs in lake sediments are estimated to be wastewater discharge, riverine inflow, and atmospheric deposition.

Novel automated identification and quantification database using liquid chromatography quadrupole time-of-flight mass spectrometry for quick, comprehensive, cheap and extendable organic micro-pollutant analysis in environmental systems.

In order to protect human health and the environment, highly efficient, low-cost, labor-saving, and green analysis of toxic chemicals are urgently required. To achieve this objective, we have developed a novel database-based automated identification and quantification system (AIQS) using LC-QTOF-MS. Since the AIQS uses retention times (RTs), exact MS and MS-MS spectra, and calibration curves of 484 chemicals registered in the database instead of the use of standards, the targets can be determined with low-cost in a short time. The AIQS uses Sequential Window Acquisition of All Theoretical Fragment-ion Spectra as an acquisition method by which we can obtain accurate MS and MS-MS spectra of all detectable substances in a sample with minimal interference from co-eluted peaks. Identification is certainly done using RTs, mass error, ion ratios (a precursor to two product ions), and accurate MS and MS-MS spectra. Consequently, the chance of misidentification is very low even in dirty samples. To examine the accuracy of the AIQS, two collaborative tests were conducted. The first test used 208 pesticide standards at two concentrations (10 and 100 ng mL-1) using 7 instruments, and showed that average trueness was 106 and 95.2%, respectively, with relative standard deviations of 90% of the test compounds below 30%. The second collaborative study involved 5 laboratories carrying out recovery tests on 200 pesticides using 10 river waters. The average recovery was 71.6%; this was 15% lower than that using purified water probably due to the matrix effects. The average relative standard deviation was 30% worse than that of measurement of the standards. Both the recovery and reproducibility, however, satisfied the criteria of Analytical Method Validity Guidelines, Ministry of Health, Labour and Welfare, Japan. Instrument detection limits of 96% of the registered compounds are below 10 pg. The AIQS allows for easy addition of new substances and retrospective analysis after their addition. The results applied to actual samples showed that the AIQS has sufficient identification and quantification performance as a target screening method for a large number of substances in environmental samples.

Occurrence, potential sources, and risk assessment of pharmaceuticals and personal care products in atmospheric particulate matter in Hanoi, Vietnam.

Pharmaceutical and personal care products (PCPPs) were recently recognized as emerging pollutants due to their potential for adverse health and environmental impacts. One potential route of exposure, atmospheric particulate matter (APM), for polar PPCP chemicals has to date received limited attention. This study screened for 190 polar PPCP chemicals in outdoor APM samples collected from two locations in Hanoi, Vietnam, and predictions of source and potential effects on human health are presented. Day and night, as well as dry and rainy seasonal samples, were taken, and samples screened by LC-TOF, using sequential window acquisition and all theoretical fragment ion spectra method. Eleven PPCP chemicals were detected above the LOD and in more than one sample. The ∑11PPCP chemicals ranged from 0.61 to 21.9 ng m-3 (median 2.07 ng m-3), with between 2 and 6 compounds identified in individual samples (median 4). The ∑11PPCP chemicals collected near a heavy traffic area was greater than that in a populated residential zone. Night concentrations were significantly greater than day in both dry and rainy seasons (p < 0.05). Butyl methoxydibenzoylmethane, benzophenone-3, acetaminophen, cotinine, and fluorescent brightener 71 were detected in > 50% of samples. These are typically found in sunscreens, cosmetics, antipyretics, tobacco, and dyes. The DIair, hazard quotient (HQ), and hazard index (HI) for adults and children at sampling sites were estimated. The HQ for both adults and children were orders of magnitude less than the risk or were close to or whichever. APM does appear to be a potential additional secondary exposure source of PPCP chemicals to the environment and more work is needed to identify if sources are local or ubiquitous and if there is a greater health risk.

Occurrence and exposure risk assessment of organic micropollutants in indoor dust from Malaysia.

Indoor dust is an important source of human exposure to hazardous organic micropollutants (OMPs) because humans spend about 90 % of their time in the indoor environments. This study initially analyzed the concentrations and compositions of OMPs in the dust of different indoor environments from Kuala Lumpur, Malaysia. A total of 57 OMPs were detected and assigned to 7 chemical classes in this study. The total concentration of OMPs ranged from 5980 to 183,000 ng/g, with the median concentration of 46,400 ng/g. Personal care products, organophosphate esters, and pesticides were the dominant groups, with their median concentrations at 12,000, 10,000, and 5940 ng/g, respectively. The concentrations and compositions of influential OMPs varied in different microenvironments, suggesting different sources and usage patterns in the house. Then, the noncarcinogenic and carcinogenic risks of exposure to these substances for diverse age groups were assessed based on the median concentration. Cumulative noncarcinogenic risks of these OMPs via ingestion pathway were estimated to be negligible (1.41 × 10-4 - 1.87 × 10-3). The carcinogenic risks of these OMPs were higher than 10-6 (1.63 × 10-6 - 6.17 × 10-6) and should be noted. Theobromine accounted for more than 89 % of the cumulative cancer risk, implying that the carcinogenic risk of theobromine needs further monitoring in the future. Toddler was the most affected group for cancer risk among all the age groups, regardless of the microenvironments. These findings from this study may provide a benchmark for future efforts to ensure the safety of indoor dust for the local residents.

Distribution and health risks of organic micropollutants from home dusts in Malaysia.

Indoor dust is an important medium to evaluate human exposure to emerging organic contaminants. The principal aim of this study was to determine overall status of organic micropollutants (OMPs) of indoor dust in Kuala Lumpur, Malaysia and assess their corresponding health risks. One hundred thirty-three OMPs, ascribed to 13 chemical groups, were screened by Automated Identification and Quantification System with a GC-MS database. The concentrations of OMPs ranged between 460 and 4000 µg/g, with the median concentration of 719 µg/g. The dominant chemical groups were ascribed to n-alkanes (median: 274 µg/g), plasticizers (151 µg/g), sterols (120 µg/g), and pesticides (42.6 µg/g). Cholestrol was the most abundant compound (median: 115 µg/g). Different sources and usage patterns of OMPs in various houses were expected. Toxicity values of OMPs were obtained from existing databases or predicted by quantitative structure-activity relationship models. Cumulative hazard quotients for OMPs through ingestion route were lower than one for all the dust samples, demonstrating that there was no remarkable non-cancer risk. The cancer risks of these OMPs were greater than 10-4, with cholestrol dominating 99.1% of the carcinogenic risks, which suggested that there was a significant cancer risk. This study might offer a benchmark to ensure the safety of chemical usages in future in Malaysia.

The rapid survey method of chemical contamination in floods caused by Typhoon Hagibis by combining in vitro bioassay and comprehensive analysis.

A novel comprehensive assessment system, consisting of a bioassay and chemical analysis, was developed to quickly evaluate the human health risk posed by toxic chemicals discharged due to natural disasters. To analyze samples quickly, a yeast-two-hybrid assay (Y2H) and GC-MS equipped with an automated identification and quantification system (AIQS-GC) were employed for the bioassay and chemical analysis, respectively. Since the analysis of 1000 substances by AIQS could be finished within two days following the Y2H assay for screening, this method would complete the risk assessment within three days. To confirm the applicability of this method in real environmental samples, we examined it using sediments circulated by Typhoon Hagibis. In one sediment sample, a distinctive response was indicated by the Y2H assay, and relatively high DDT concentration was identified by AIQS-GC in the same sediment. Therefore, using the results obtained from this method, a human health risk assessment of DDT was conducted, which indicated that the risk could be ignored. Additionally, the contamination of PAHs and alkanes was suggested as well. In this study, the pollution risk assessment could be completed within three days. Therefore, to our knowledge, this is the first study to demonstrate an assessment system with a rapid combination method for emergencies. Consequently, it is believed that this type of novel system would be needed in the future due to the increasing number of natural disasters predicted worldwide.

Comprehensive analyses of agrochemicals affecting aquatic ecosystems: A case study of Odonata communities and macrophytes in Saga Plain, northern Kyushu, Japan.

The negative influence of agrochemicals (pesticides: insecticide, fungicide, and herbicide) on biodiversity is a major ecological concern. In recent decades, many insect species are reported to have rapidly declined worldwide, and pesticides, including neonicotinoids and fipronil, are suspected to be partially responsible. In Japan, application of systemic insecticides to nursery boxes in rice paddies is considered to have caused rapid declines in Sympetrum (Odonata: Libellulidae) and other dragonfly and damselfly populations since the 1990s. In addition to the direct lethal effects of pesticides, agrochemicals indirectly affect Odonata populations through reductions in macrophytes, which provide a habitat, and prey organisms. Due to technical restrictions, most previous studies first selected target chemicals and then analyzed their influence on focal organisms at various levels, from the laboratory to the field. However, in natural and agricultural environments, various chemicals co-occur and can act synergistically. Under such circumstances, targeted analyses might lead to spurious correlations between a target chemical and the abundance of organisms. To address such problems, in this study we adopted a novel technique, "Comprehensive Target Analysis with an Automated Identification and Quantification System (CTA-AIQS)" to detect wide range of agrochemicals in water environment. The relationships between a wide range of pesticides and lentic Odonata communities were surveyed in agricultural and non-agricultural areas in Saga Plain, Kyushu, Japan. We detected significant negative relationships between several insecticides, i.e., acephate, clothianidin, dinotefuran, flubendiamide, pymetrozine, and thiametoxam (marginal for benthic odonates) and the abundance of lentic Epiprocta and benthic Odonates. In contrast, the herbicides we detected were not significantly related to the abundance of aquatic macrophytes, suggesting a lower impact of herbicides on aquatic vegetation at the field level. These results highlight the need for further assessments of the influence of non-neonicotinoid insecticides on aquatic organisms.

Occurrence and risk assessment of herbicides and fungicides in atmospheric particulate matter in Hanoi, Vietnam.

Vietnam is a Southeast Asian developing country with rapidly increasing air pollution, especially in large cities. Over 350,000 chemicals and chemical mixtures are produced and used in Vietnam; however, the country has only implemented air quality standards for 44 substances, which are primarily focused on inorganic and volatile organic compounds. Although numerous pesticides are frequently applied across large cities in Vietnam, information on their concentrations in atmospheric particulate matter (APM) is limited. Therefore, to investigate their occurrence and health effects, 187 pesticides in APM were screened using the liquid chromatography-mass spectrometry-quadrupole time of flight- Sequential Window Acquisition of All Theoretical Fragment Ion Spectra method (LC-QTOF-MS-SWATH). A total of 22 pesticides (16 fungicides and 6 herbicides) were quantified in the dry and rainy seasons. Among them, 19 substances were quantified in APM for the first time in Vietnam. Their median total concentrations in the dry season were higher than those in the rainy season, and the concentrations in the daytime were one-third of the night-time concentrations in both seasons. Their total levels ranged from 0.82 to 21.1 ng m-3 (median, 3.63 ng m-3), the detection frequencies of 9 pesticides were higher than 70%, and 7-14 pesticides were detected per sample (median, 10). Some of the detected pesticides were likely sourced from their prevalent use in amenity turf protection (e.g., in parks and public roads) and weed control (e.g., in gardens, floriculture, and agriculture). The total daily intake (DIair) values for adults, children, and infants were 8.17E-06, 2.06E-05, and 2.45E-05 mg kg-1 d-1, respectively, and the highest Hazard Quotients (HQs) were 4.81E-04, 1.22E-03, and 1.44E-03, respectively. All HQs and HIs of the pesticides were < 1 for all population groups (adults, children, and infants), indicating negligible exposure risks.

Comprehensive study of insecticides in atmospheric particulate matter in Hanoi, Vietnam: Occurrences and human risk assessment.

Air pollution is the most serious environmental issue in Vietnam, particularly in big cities. Air pollutants that are set as environmental standards are regularly monitored by the public institutions. Whereas, environmental data on organic micro-pollutants in atmospheric particulate matters (APMs) is limited, including PAHs and POPs. Although massive pesticides are used in big cities, their data in APMs in Vietnam is very scarce. In order to elucidate their occurrence in the ambient air in Hanoi and their health effects, we surveyed 107 insecticides in APMs by a novel target screening method using LC-QTOF-MS-SWATH. A total of 19 insecticides were detected in the dry and the rainy seasons. Among them, 16 substances are, to our knowledge, reported for the first time in the literature. Their total concentrations varied from 0.47 to 27.0 ng m-3 (median, 3.6 ng m-3), detection frequencies of 12 compounds are higher than 42%, and the number of insecticides detected per each sample ranging from 5 to 13 (median, 9). Total concentrations in the dry season were generally higher than in the rainy season, and concentrations at night were higher than daytime in both seasons. The level of insecticides depends not only on the season, but also on its physicochemical properties, its application conditions, and the meteorological conditions. Their emission sources could be related to agricultural usage, floricultural activities, and pest control in houses. The total maximum daily intake (DIair) through inhalation for adults and children were 2.39E-05 mg kg-1 d-1 and 2.98E-05 mg kg-1 d-1, respectively. The highest Hazard Quotients (HQs) were 1.34E-03 and 3.37E-03, and the highest Hazard Indices (HIs) were 2.71E-03 and 6.33E-03 for adults and children, respectively. All values of HQs, and HIs of insecticides were less than 1, indicating that health risk would be negligible.

Evaluation of identification accuracy using AIQS for GC-MS for measuring heavily contaminated samples.

Automated identification and quantification systems with gas chromatography-mass spectrometry (GC-MS) (i.e., AIQS-GC) are used as a simple and comprehensive method for screening chemicals existing in the environment and are expected to be useful for emergency surveys in the event of a disaster. However, reports on the potential of AIQS-GC in heavily contaminated samples (HCSs) are limited. In this study, the identification performance of AIQS-GC was confirmed by comparing the exact mass of the targets identified by AIQS-GC with the measured accurate mass using GC-quadrupole-time-of-flight MS (GC-QTofMS) and by employing firefighting wastewater as HCS. In HCS, the mass spectrum interference was determined to cause false positives. The GC-QTofMS method revealed the presence of false positives and the false rate of AIQS-GC in HCS. Herein, AIQS-GC showed high identification accuracy in a normal sample such as river water. Conversely, in HCS, AIQS-GC may lead to incorrect evaluations. The combination of AIQS-GC and support method using GC-QTofMS, which can avoid the false positive is extremely useful for the rapid and easy analysis of HCS.

Development of a rapid and comprehensive method for identifying organic micropollutants with high ecological risk to the aquatic environment.

Currently, tens-of-thousands of chemicals are used in Japan, and their presence in and impact on aquatic ecosystems are poorly understood. Because conventional risk evaluation processes using target analysis and biological tests are time-consuming and costly, it is challenging to investigate all substances. Therefore, we aimed to develop a rapid and highly efficient screening scheme for identifying hazardous organic micropollutants (OMPs) in aquatic ecosystems. The scheme is divided into two steps: chemical analysis and risk evaluation. First, a comprehensive screening method (CSM) using gas chromatography (GC)-mass spectrometry (MS) and a database containing nearly 1000 compounds is used to identify known compounds, and nontargeted analysis is carried out using a GC × GC-time-of-flight (TOF)MS to detect compounds not registered in the database. Secondly, the predicted toxicity values obtained by quantitative structure-activity relationship (QSAR) are used to evaluate and rank the ecological risk of each detected OMPs and to identify priority compounds for detailed survey. To assess the proposed scheme, we surveyed representative urban rivers in Japan and ranked the potential toxicity of the identified compounds. The total number of compounds detected in water from each river ranged from 29 to 87, and the total concentrations ranged from 2.3 to 63 µg L-1. Pharmaceuticals and personal care products, such as crotamiton and galaxolide, were identified in the urban rivers and found to have high ecotoxicity rankings. Thus, the scheme combining CSM and risk evaluation using QSAR is a novel screening that can identify candidates with high ecological risk in aquatic environment rapidly and efficiently.

Quinolone Signals Related to Pseudomonas Quinolone Signal-Quorum Sensing Inhibits the Predatory Activity of Bdellovibrio bacteriovorus.

Bdellovibrio bacteriovorus is one of the predatory bacteria; therefore, it can act as a novel "living antibiotic," unlike the current antibiotics. Here the predation of Escherichia coli by B. bacteriovorus was inhibited in the presence of Pseudomonas aeruginosa. This study investigated whether P. aeruginosa-induced predation inhibition is associated with bacterial quorum sensing (QS). Each las, rhl, or pqs QS mutant in P. aeruginosa was used to check the predatory activity of E. coli cells using B. bacteriovorus. As a result, the predatory activity of B. bacteriovorus increased in a mutant pqs QS system, whereas wild-type PA14 inhibited the predatory activity. Moreover, the addition of 4-hydroxy-2-heptylquinoline (HHQ) or the analog triggered the low predatory activity of B. bacteriovorus and killed B. bacteriovorus cells. Therefore, a defensive action of P. aeruginosa against B. bacteriovorus is activated by the pqs QS system, which produces some quinolone compounds such as HHQ.

Occurrence and ecological risks of 156 pharmaceuticals and 296 pesticides in seawater from mariculture areas of Northeast China.

China is the largest mariculture producer in the world. In recent years, pharmaceuticals and pesticides have been widely used in mariculture activities; however, most studies have only focused on the occurrence of limited types of antibiotics and organochlorine pesticides. It is critical to comprehensively investigate the occurrence of pharmaceuticals and pesticides in mariculture areas and assess their potential impacts on ocean ecosystems. In this study, the occurrence, distribution, and ecological risk of 484 compounds, including 296 pesticides, 156 pharmaceuticals, and 32 other substances, in the drainage ditches of culture ponds and raft-culture areas were investigated. A total of 51 compounds were detected in the mariculture area, with total concentrations ranging from 5.4 × 102 to 2.0 × 104 ng/L at each sampling site. Eleven pesticides, three pharmaceuticals, and five other compounds were detected with detection frequencies of 100%. The cluster analysis indicated that mariculture is a source of herbicide pollution in coastal waters. To assess the ecological risks of the detected compounds, toxicity data collected from the database and predicted from quantitative structure activity relationship (QSAR) models were used to calculate the risk quotients and probabilistic risks. According to the risk quotients, five pollutants, including diuron, ametryn, prometryne, simetryn, and terbutryn, were estimated to pose high risks to marine organisms. The results of the probabilistic risk assessment indicated that only diuron, a biocide used in antifouling paint and mariculture, would have an adverse effect on up to 8% of the aquatic species in nearshore areas. These findings could be helpful in determining the aquatic benchmarks of pesticides and pharmaceuticals in mariculture discharge to promote the sustainable development of mariculture and ecological protection in coastal areas.