Investigation of variability in the matrix effect on stable isotope-labeled internal standards in liquid chromatography-tandem mass spectrometry analysis of 25 pesticides in vegetables.

The matrix effects (ME) in simultaneous analysis of pesticide residue using liquid chromatography-tandem mass spectrometry (LC-MS/MS) were evaluated by comparing the slopes of matrix-matched and reagent-only calibrations of four types of vegetable samples. Both the sampling and measurement variances of the ME were also determined using one-way analysis of variance. Substantial ion suppression (ME<-20%) was observed in komatsuna, spinach, and tomato when a modified Japanese official method was implemented. The ME magnitude varied significantly due to sample variability for some pesticides, but it varied by no more than 4% as a result of analytical procedure variance. This study also showed that the addition of stable isotope-labeled internal standards at low concentrations improved the recovery of pesticides from samples at various residue levels. The findings of this study highlight the importance and practical application of internal standards and the matrix-matched calibration method in residue analysis using LC-MS/MS.

Enhancement of photodegradation of polyethylene with adsorbed polycyclic aromatic hydrocarbons under artificial sunlight irradiation.

The photodegradation of plastic waste produces microplastics (MPs) in marine environments. Plastics can adsorb hydrophobic organic pollutants such as polycyclic aromatic hydrocarbons (PAHs) and can be transported over long distances. However, the impact of adsorbed pollutants on the photodegradation remains unknown. Here, we show that adsorbed PAHs act as photocatalysts that promote the photodegradation of polyethylene. Upon light irradiation, coloration and surface degradation of the PAH-adsorbed polyethylene sheets were observed, indicating that the PAH-adsorbed polyethylene sheets are less resistant to light. Furthermore, fluorene, phenanthrene, anthracene, benzo[a]anthracene, benzo[a]pyrene, and indeno[1,2,3-cd]perylene adsorbed on polyethylene MP exhibited lower photodegradation rates than the aqueous phase. These results indicate that these PAHs can act as photocatalysts; their role of PAHs may have two adverse effects on marine environment. First, enhanced photodegradation of plastic waste increased the production of MPs. Second, the lifetime of PAHs is extended, thereby enhancing PAHs pollution in marine environments.

Development of a New Polar Organic Chemical Integrative Sampler for 1,4-dioxane Using Silicone Membrane as a Diffusion Barrier.

Efficient monitoring methods must be developed for 1,4-dioxane, which is suspected to be carcinogenic to humans and is highly mobile in aquatic environments. In this regard, polar organic chemical integrative samplers (POCIS) have been utilized extensively as passive samplers for determining time-weighted average concentrations of hydrophilic organic compounds. However, POCIS are difficult to apply to extremely hydrophilic known organic compounds with negative log octanol-water partition coefficient (Kow ) values due to their limited kinetic sampling time. Using an activated carbon-based sorbent with a high adsorption capacity and a bilayer of silicone and polyethersulfone membranes that inhibit mass transfer to the sorbent, we developed a POCIS device to measure 1,4-dioxane (log Kow -0.27) in the present study. Permeation and field calibration tests demonstrated that the use of silicone membranes effectively reduces the water-to-sorbent mass transfer rate. The sampling rate and kinetic sampling period determined by field calibration tests were 1.4 ml day-1 and >14 days, respectively. Finally, the developed POCIS device was applied to a landfill treatment plant to determine the 1,4-dioxane concentrations. Environ Toxicol Chem 2023;42:296-302. © 2022 SETAC.

Comparative Evaluation of the Polar Organic Chemical Integrative Sampler in Two Types of Validation Systems Simulating Peak Concentration Events.

Polar organic chemical integrative sampler (POCIS) devices have been suggested for measuring time-weighted averages (TWAs) of contaminant concentrations resulting from chemical leak accidents in aquatic environments. However, the response of the POCIS device in the emergency condition in natural water remains unclear. The response of the POCIS device to contaminant fluctuation was investigated using a chamber test with tap water and a channel test with natural water. The fluctuation in the chamber and the channel simulated the condition of river water under a chemical leak scenario (maximum concentration: 1-10 µg L-1 , half-life: 1 day). The target chemicals were neonicotinoid pesticides (dinotefuran, clothianidin, thiamethoxam, imidacloprid, acetamiprid, and thiacloprid) and bisphenol A. The ratio of the POCIS measured value to the TWA values of grab samplings (POCIS/TWA) for the channel test (temperature: 15 °C, flow velocity: 15 cm s-1 ) ranged from 61% (clothianidin) to 133% (thiacloprid). The results indicated that the POCIS device could be effectively used as a monitoring device in an aquatic environment under the chemical leak scenario over a time period of more than14 days. In addition, the POCIS/TWA ratios obtained from the chamber test and the channel test were in the range of 50-150%. Thus, the chamber test could be used to evaluate the POCIS device at a low cost. Environ Toxicol Chem 2021;40:3010-3018. © 2021 SETAC.

Photolysis of polycyclic aromatic hydrocarbons adsorbed on polyethylene microplastics.

Contaminants adsorbed on microplastics (MPs) are a potential risk to aquatic environments. Several studies have demonstrated that polycyclic aromatic hydrocarbons (PAHs), which adsorb on MPs, can be photolyzed in aqueous solutions. We investigated photolysis of PAHs on MPs under sunlight conditions to estimate their environmental fate for the first time. The PAHs (25 ng each) were added to polyethylene powder, which was used as the MP sample. The MP sample was agitated in water with sunlight irradiation; thereafter, the concentration of the PAHs on the MP sample was determined by high-pressure liquid chromatography with a fluorescence detector. The half-life values of the PAHs were estimated between 3.4 × 102 (pyrene) and 3.2 × 104 min (benz[j]fluoranthene). These values are 0.5 (fluoranthene) to 25 (benzo[a]pyrene) times larger than those in the aqueous phase. Additionally, the degradation of PAHs by OH radicals produced by the photolysis of nitrate was observed.

Treatment of 1,4-dioxane-containing water using carriers immobilized with indigenous microorganisms in landfill leachate treatment sludge: A laboratory-scale reactor study.

1,4-Dioxane (DX) is a contaminant of emerging concern in aquatic environments, and is frequently found in landfill leachate. As a biological method applicable to landfill leachate treatment facilities, the feasibility of DX treatment using carriers immobilized with microorganisms indigenous to landfill leachate treatment sludge was explored through laboratory-scale reactor experiments by introducing carriers prepared via microorganism immobilization in the aeration tank of a leachate treatment facility. Three different carrier materials were used to immobilize microorganisms, and a model DX-containing water (10 mg/L) was treated under continuous feeding. Biological DX removal to < 0.5 mg/L was achieved using all carrier types, thereby adhering to the effluent standard for landfill leachate in Japan, which confirms the usefulness of the proposed method. However, weaker aeration and enhanced DX loading drastically impaired the DX removal performance depending on the carrier materials. This suggests the importance of carrier selection and control of the operational variables to ensure stable and effective DX removal. Microbial community analyses revealed that Pseudonocardia with thm genes may largely contribute to the initial oxidation of DX, irrespective of the carrier type, suggesting the importance of this population for the continuous treatment of low DX concentrations with mixed microbial consortia.

Development and Calibration of the Polar Organic Chemical Integrative Sampler (POCIS) for Neonicotinoid Pesticides.

Neonicotinoid pesticides are highly hydrophilic systemic insecticides that have been extensively used worldwide. To evaluate their environmental risks, the concentrations of these pesticides in the aquatic environment must be monitored. Although the polar organic chemical integrative sampler (POCIS) has proved to be a suitable passive sampler for many highly hydrophilic compounds, Oasis HLB (Waters) POCIS has shown limitations for the monitoring of neonicotinoid pesticides, such as short linear uptake ranges. In the present study we optimized POCIS for neonicotinoid pesticides by selecting suitable adsorbents and filters. The ENVI-Carb (Supelco) nonporous carbon-based adsorbent demonstrated a good balance between strong sorption and high recovery. Static renewal experiments showed that the our POCIS device using ENVI-Carb with a polyethersulfone membrane filter had a 3 d (dinotefuran) to 28 d (clothianidin, imidacloprid, acetamiprid, and thiacloprid) linear range, which is longer than that of HLB POCIS (≤1 [dinotefuran] to 14 d). The POCIS using ENVI-Carb with a polytetrafluoroethylene membrane had higher sampling rates (0.270 L/d [clothianidin] to 0.686 [imidacloprid] L/d) than those of the HLB POCIS for short-term deployment. The time-weighted average concentrations in actual river water measured by the new POCIS were in good agreement with those obtained by repeated grab sampling, within 30%. Moreover, POCIS detected 2 neonicotinoid pesticides that were not detected by grab sampling. Thus, the proposed POCIS is a promising tool for the monitoring of neonicotinoid pesticides. Environ Toxicol Chem 2020;39:1325-1333. © 2020 SETAC.

Simultaneous analysis of seven neonicotinoid pesticides in agricultural products involving solid-phase extraction and surrogate compensation using liquid chromatography-tandem mass spectrometry.

This study proposes a practical and precise method for the simultaneous analysis of seven neonicotinoid pesticides in agricultural products using liquid chromatography-tandem mass spectrometry from two different approaches. First, the applicability of a cleanup cartridge, comprised of a polymer sorbent consisting of a styrene-divinylbenzene copolymer with N-containing polar groups and methacrylate, in food samples was demonstrated for the first time. Second, applying an internal standard (IS) calibration method at a lower cost was considered by changing the timing of the IS addition and selecting the minimum number of ISs by referring on the matrix effect. The proposed method resulted in excellent recoveries in all tested matrices (brown rice, grapes, and peanuts) at a spiked concentration of 0.01 mg/kg. Subsequently, a residue analysis of hagobou (young burdock) was conducted. Imidacloprid was detected at 0.02 mg/kg, and the recoveries calculated in parallel with the analysis were satisfactory.

Carbon sources that enable enrichment of 1,4-dioxane-degrading bacteria in landfill leachate.

1,4-Dioxane (DX) is a recalcitrant cyclic ether that has gained attention as an emerging pollutant in the aquatic environment. Enrichment of indigenous DX-degrading bacteria, which are considered to be minor populations even in DX-impacted environments, is the key for efficient biological DX removal. Therefore, this study aimed to explore carbon sources applicable for the enrichment of DX-degrading bacteria present in landfill leachate, which is a potential source of DX pollution. Microorganisms collected from landfill leachate were cultivated on six different carbon sources (DX, tetrahydrofuran (THF), 1,3,5-trioxane (TX), ethylene glycol (EG), diethylene glycol (DEG), and 1,4-butanediol (BD)) in a sequential batch mode. Consequently, enrichment cultures cultivated on THF in addition to DX improved the DX degradation ability compared to that of the original leachate sample, while those on the other test carbon sources did not. The results indicated that THF can be an alternative carbon source to enrich DX-degrading bacteria, and that TX, EG, DEG and BD are not applicable to concentrate DX-degrading bacteria in complex microbial consortia. In addition, sequencing analyses of 16S rRNA and soluble di-iron monooxygenase (SDIMO) genes revealed notable dominance of thm/dxm genes involved in group 5 SDIMO both in DX- and THF-enrichment cultures. The analysis also showed a predominance of Pseudonocardia in THF-enrichment culture, suggesting that Pseudonocardia harboring thm/dxm genes contributes to enhanced DX degradation in THF-enrichment culture.

Reduced bioavailability of polycyclic aromatic hydrocarbons (PAHs) in sediments impacted by carbon manufacturing plant effluent: Evaluation by ex situ passive sampling method.

Potential risks of polycyclic aromatic hydrocarbons (PAHs) in sediments of a Japanese bay contaminated by carbon manufacturing plant effluent were evaluated by calculating toxicity units (TUs). TUs calculated from the measured whole-sediment concentrations (Cwhole) were often higher than or close to 1, signaling a possible toxicity concern to benthic organisms. In contrast, TUs based on the freely dissolved pore water concentrations (Cfree) measured by an ex-situ passive sampling method with polyethylene strips were 0.0007-0.005, much lower than 1, indicating no effect. We also found that the fractions of black carbon in sediments of the contaminated bay were significantly higher than those of reference sites. Overall, we conclude that carbon manufacturing plant effluent substantially increases Cwhole of PAHs in sediments but also increases the fraction of carbonaceous particles that strongly retain PAHs. As a combined result, bioavailable concentrations (as expressed by pore water Cfree) of PAHs do not increase as much as Cwhole. The results of this study indicate that ecotoxicological risks of PAH contamination by carbon manufacturing plants should be evaluated by directly measuring pore water Cfree instead of Cwhole.

Determining the suitability of a polar organic chemical integrated sampler (POCIS) for the detection of pesticide residue in the Ishikawa River and its tributary in Osaka, Japan.

The monitoring of pesticide concentrations in Japanese rivers was conducted via a grab sampling method and a passive sampling method using the polar organic chemical integrated sampler (POCIS). The results showed that cumulative detections were 84 with grab sampling and 98 with the POCIS. All of the pesticides detected by grab sampling could be quantified with a POCIS except for one (although its traces were detected). In addition, 15 detections quantified by POCIS were undetected by grab sampling. The average concentrations of pesticides detected by both the POCIS and grab sampling during the investigation period were compared. A good correlation was observed between the two methods with a slope of 1.00 and a coefficient of correlation (r) of 0.897 (n=79). Although high temporal variability was observed in the pesticide concentrations by grab sampling, the average pesticide concentrations obtained by the two methods showed similar values during the investigation period.

Impact of aerobic acclimation on the nitrification performance and microbial community of landfill leachate sludge.

Nitrogenous pollution of water is regarded as a global environmental problem, and nitrogen removal has become an important issue in wastewater treatment processes. Landfill leachate is a typical large source of nitrogenous wastewater. Although the characteristics of leachate vary according to the age of the landfill, leachates of mature landfill have high concentrations of nitrogenous compounds. Most nitrogen in these leachates is in the form of ammonium nitrogen. In this study, we investigated the bacterial community of sludge from a landfill leachate lagoon by pyrosequencing of the bacterial 16S rRNA gene. The sludge was acclimated in a laboratory-scale reactor with aeration using a mechanical stirrer to promote nitrification. On 149 days, nitrification was achieved and then the bacterial community was also analyzed. The bacterial community was also analyzed after nitrification was achieved. Pyrosequencing analyses revealed that the abundances of ammonia-oxidizing and nitrite-oxidizing bacteria were increased by acclimation and their total proportions increased to >15% of total biomass. Changes in the sulfate-reducing and sulfur-oxidizing bacteria were also observed during the acclimation process. The aerobic acclimation process enriched a nitrifying microbial community from the landfill leachate sludge. These results suggested that the aerobic acclimation is a processing method for the nitrification ammonium oxidizing throw the enrichment of nitrifiers. Improvement of this acclimation method would allow nitrogen removal from leachate by nitrification and sulfur denitrification.

Comparing polyethylene and polyoxymethylene passive samplers for measuring sediment porewater concentrations of polychlorinated biphenyls: Mutual validation and possible correction by polymer-polymer partition experiment.

Two sediment passive samplers, polyethylene (PE) and polyoxymethylene (POM), were compared and mutually validated for measuring freely dissolved concentrations (Cfree) of polychlorinated biphenyls (PCBs) in sediment porewater. PE and POM strips in commonly used dimensions (30 and 76 µm in thickness, respectively) were exposed to sediment slurries for 28 d. The Cfree values calculated using literature polymer-water partition coefficients were consistently higher for PE than for POM by a factor of 2 on average. Time series experiments over 96 d show that 28 d are sufficient for attaining partition equilibrium of PCBs for PE, whereas even 96 d may not be enough for POM. To gain additional insight, POM and PE strips were co-exposed to bovine serum albumin suspension spiked with PCBs. The POM/PE concentration ratios increased over 56 d, and the ratios at 28 d were in agreement with the POM-to-PE ratios of PCB concentrations from the 28-d sediment slurry experiments. This agreement suggests that the use of apparent POM-water partition coefficients (i.e., non-equilibrium concentration ratios) suitable for a 28-d exposure to sediment slurries may correct the non-attainment of equilibrium and could provide more accurate Cfree values.

Temperature dependence on the pesticide sampling rate of polar organic chemical integrative samplers (POCIS).

Laboratory experiments were performed to determine the sampling rates of pesticides for the polar organic chemical integrative samplers (POCIS) used in Japan. The concentrations of pesticides in aquatic environments were estimated from the accumulated amounts of pesticide on POCIS, and the effect of water temperature on the pesticide sampling rates was evaluated. The sampling rates of 48 pesticides at 18, 24, and 30 °C were obtained, and this study confirmed that increasing trend of sampling rates was resulted with increasing water temperature for many pesticides.