Ongoing Laboratory Performance Study on Chemical Analysis of Hydrophobic and Hydrophilic Compounds in Three Aquatic Passive Samplers.

The quality of chemical analysis is an important aspect of passive sampling-based environmental assessments. The present study reports on a proficiency testing program for the chemical analysis of hydrophobic organic compounds in silicone and low-density polyethylene (LDPE) passive samplers and hydrophilic compounds in polar organic chemical integrative samplers. The median between-laboratory coefficients of variation (CVs) of hydrophobic compound concentrations in the polymer phase were 33% (silicone) and 38% (LDPE), similar to the CVs obtained in four earlier rounds of this program. The median CV over all rounds was 32%. Much higher variabilities were observed for hydrophilic compound concentrations in the sorbent: 50% for the untransformed data and a factor of 1.6 after log transformation. Limiting the data to the best performing laboratories did not result in less variability. Data quality for hydrophilic compounds was only weakly related to the use of structurally identical internal standards and was unrelated to the choice of extraction solvent and extraction time. Standard deviations of the aqueous concentration estimates for hydrophobic compound sampling by the best performing laboratories were 0.21 log units for silicone and 0.27 log units for LDPE (factors of 1.6 to 1.9). The implications are that proficiency testing programs may give more realistic estimates of uncertainties in chemical analysis than within-laboratory quality control programs and that these high uncertainties should be taken into account in environmental assessments.

Development of a safety analysis method for volatile organic compounds using 2-phenoxyethanol as solvent.

Indoor volatile organic compounds (VOCs) are usually sampled using active carbon samplers and subsequently analyzed using gas chromatography-mass spectrometry (GC-MS) to assess the exposure risk to workers. Therefore, selection of a suitable solvent for VOC extraction is crucial. However, reports on the use of 2-phenoxyethanol-known for its low vapor pressure and low toxicity-as a solvent for extracting VOCs from activated carbon are lacking. Here, we show that 2-phenoxyethanol is a suitable alternative solvent with low toxicity and can extract a wide variety of VOCs without overlapping with target VOCs on the gas chromatogram. The recoveries of 2-phenoxyethanol were 57% (styrene) to 83% (methyl n-butyl ketone), which were higher than those of CS2, acetone, and n-hexane at room temperature. The recoveries improved to 67% (styrene) to 102% (isopentyl acetate) under 50 °C. Optimization of the GC conditions showed that a viscosity delay time of 3 s was required to avoid producing bubbles in the injection syringes. We selected DB-HeavyWAX as a column because it could be heated above the boiling point of 2-phenoxyethanol (247 °C), allowing the removal of 2-phenoxyethanol from the column. This study contributes to the development of analysis methods for VOCs under safe operating conditions.

Development of an analytical method for indoor polycyclic aromatic hydrocarbons and their halogenated derivatives by using thermal separation probe coupled to gas chromatography-tandem mass spectrometry.

Polycyclic aromatic hydrocarbons (PAHs) and their halogenated derivatives (XPAHs) have been a concern because of their high toxicity. Monitoring indoor PAHs and XPAHs concentrations is important for risk assessment because humans typically spend >90 % of their time indoors. However, the background levels of indoor PAHs and XPAHs concentrations are unknown because of the low sensitivity of conventional analytical methods. In this study, we developed a highly sensitive analytical method using a thermal separation probe (TSP) coupled to a gas chromatograph with a triple quadrupole mass spectrometer method for 26 PAHs and 40 XPAHs. The method quantification limit (MQL) values of the TSP method were 1.1 (3,8-dichlorofluoranthene)-906 (dibenzo[a,e]pyrene) times lower than those of the conventional method. The regression line comparing the TSP and conventional methods was y = (0.944 ± 0.0401)x, which was in good agreement. These results demonstrate that the TSP method can be applied to indoor air analysis. The total concentrations of PAHs and XPAHs were 944 and 73.5 pg m-3 for the house and 735 and 0.924 pg m-3 in the office, respectively. Among the detected compounds, 13 PAHs and XPAHs could not be detected using conventional methods because of their high MQL values. The composition of total toxicity equivalency values in the house was dominated by dibenzo[a,i]pyrene (DBaiP: 43.2 %) and dibenzo[a,h]pyrene (DBahP: 27.1 %), which could not be detected using the conventional method. Therefore, the TSP method can improve the risk assessment of indoor PAHs and XPAHs.

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.

Spatiotemporal distribution and pollution assessment of trace metals in the Buriganga River, Bangladesh.

The Buriganga River plays a key role in the socioeconomic structure of Dhaka, the capital of Bangladesh. However, this river is severely polluted and is considered one of the most polluted in the world. Therefore, this study aimed to assess the concentrations of various metals in the Buriganga River. A study was conducted from August 2019 to February 2020 to determine the concentrations of 16 metals in water samples (n = 210) collected from 10 distinct sites in the Buriganga River. The mean values for the concentrations of Cr, Mn, Ni, Zn, As, Se, Cd, Sb, and Pb in river water were above the guideline values prescribed by the WHO, Japan, and Bangladesh. Moreover, the fraction ratios of Be, Cr, Co, Ni, Cu, Zn, Se, Mo, Ag, Cd, Sb, and Pb were high (>0.85); consequently, these metals could accumulate at high concentrations in river sediments. Assessment using the single-factor pollution index allowed the classification of the pollution level as 'serious pollution' for Sb and 'heavy pollution' for Cd, Ni, and Pb. The trace metal concentrations in this river imply that crops cultivated along the river using river water may also be contaminated with trace metals.

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.

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.

Characteristics of ammonia gas and fine particulate ammonium from two distinct urban areas: Osaka, Japan, and Ho Chi Minh City, Vietnam.

Continuous and simultaneous measurements of ammonia gas (NH3) and fine particulate ammonium (PM2.5NH4+) were performed in two distinct urban areas: Osaka, Japan, and Ho Chi Minh City (HCMC), Vietnam. Measurements were performed using a new online instrument. Two measurement periods were conducted during February 11-March 12, 2015 (cold period), and July 1-September 14, 2015 (warm period), at the urban site in Osaka, while 17 days of measurements, from May 21 to June 8, 2015, were conducted at the urban site in HCMC. The average NH3 concentration at the HCMC site was much higher than that at the Osaka site. The differences in the NH3 levels between the two cities are a result of their different emission sources. Traffic emission is a significant contributor to the NH3 levels within the urban area in Osaka. Conversely, the contribution of traffic emission to the NH3 levels in the HCMC urban area is negligible. With a population of around 8.5 million people living in the urban area of HCMC, the high NH3 level is due to human sources and poor waste management systems, especially because of the high temperature (30 °C) and dense population of the city (density up to 42,000 inhabitants per km2). In contrast to the NH3 levels, the highest PM2.5NH4+ level occurred during the cold period at the Osaka site, and the average level at this site was higher than that at the HCMC site. The availability of atmospheric acids, low temperature, and high humidity facilitates the formation of ammonium. Our results indicate that NH3 plays a key role in secondary inorganic aerosol formation; therefore, it contributes to a significant amount of PM2.5 at the Osaka site. In contrast, the high levels of PM2.5 observed at the HCMC site are likely from road traffic emission, mainly motorcycles, rather than secondary inorganic aerosol formation.