Environmental Science and Pollution Research

Kojima, Hiroyuki; Takeuchi, Shinji; Iida, Mitsuru; Nakayama, Shoji; Shiozaki, Takuya

doi: 10.1007/s11356-015-4662-9pmid: 26087926

In developing countries in Asia, such as China, Vietnam, and Thailand, there is a strong need for the development of relatively rapid and low-cost bioassays for the determination of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs) in environmental and food samples. These compounds are known to induce a variety of toxic and biological effects through their ligand-specific binding of the aryl hydrocarbon receptor (AhR). Indeed, several AhR-mediated reporter gene assays are widely used as prescreening tools for high-resolution gas chromatography/high-resolution mass spectrometry (HRGC-HRMS) analysis, which individually measures 17 PCDD/Fs and 12 DL-PCBs. In 2008, we have developed a new sensitive and rapid reporter gene assay using a genetically engineered stable cell line, designated DR-EcoScreen cells. The DR-EcoScreen assay using these cells has a number of great advantages of its sensitivity to 2,3,7,8-tetrachlorodibenzo-p-dioxin and its simple procedure, which shows little variance in the data (within CV 10 %) compared to other reporter gene assays. In this review, we summarize the application of the DR-EcoScreen assay to the determination of PCDD/Fs and DL-PCBs in ambient air samples, in fish and shellfish samples, and in flue gas samples from incinerators and provide potential usefulness of this bioassay for the determination of PCDD/Fs and DL-PCBs in various matrices.

Takeuchi, Shinji; Tanaka-Kagawa, Toshiko; Saito, Ikue; Kojima, Hiroyuki; Jin, Kazuo; Satoh, Masayuki; Kobayashi, Satoshi; Jinno, Hideto

doi: 10.1007/s11356-015-4858-zpmid: 26099596

A variety of chemicals have been used in a wide range of indoor materials, such as wallpaper and furniture, and some of them are released into the indoor air. The level of consumption as well as the diversity of these chemicals has been increasing. The particle size of the materials in the air is known to affect the depth of human exposure, e.g., particles >10 μm can only reach the nasal cavity, whereas particles 2.5–10 μm can reach the respiratory tract and particles <2.5 μm can reach the bottom of the lungs. However, information on the concentrations and form of these chemicals in indoor air is very limited. In this study, we measured 54 compounds, including plasticizers (phthalates, adipates, and others) and organophosphorus flame retardants, in indoor air samples from the living rooms of 21 dwellings in 11 prefectures across Japan. For sampling, we used a four-stage air sampler (multi-nozzle cascade impactor) equipped with three quartz fiber filters to capture chemical particulates in three size ranges (<2.5, 2.5–10, and >10 μm) and a C18 solid-phase extraction disk to capture chemicals that exist in a gas phase in indoor air. Each of the chemicals in the three particulate phases and single gas phase was extracted by acetone and measured separately using GC/MS. Of the 54 compounds tested, 37 were detected in the indoor air samples. The highest concentration observed was that of 2-ethyl-1-hexanol (5.1 μg/m3), which was detected in samples from all 21 houses. The 37 compounds were captured in the four fractions at different rates roughly based on their molecular sizes. Compounds with a smaller molecular size were commonly detected as a gas phase, whereas compounds with a larger molecular size were detected as one or more of the three particulate phases in the indoor air samples. Among the three particulate phases, many of the compounds were detected from the filter capturing the smallest (<2.5 μm) particles. Therefore, these results suggest that the chemicals measured in this study might penetrate deeply into the lungs as many of them tend to exist as a gas and/or as particles smaller than 2.5 μm.

Nakano, Toshiki; Hayashi, Satoshi; Nagamine, Norimi

doi: 10.1007/s11356-015-4898-4pmid: 26111749

Fish are exposed to a wide variety of environmental stressors, such as chemicals and acute changes in temperature. Oxytetracycline (OTC) has been used as an antibiotic for many kinds of bacterial diseases in cultured fish, but excessive doses of OTC are known to cause side effects in fish and can have negative effects on their environment. In the present study, we examined stress-related biomarker expression in response to excessive doses of dietary OTC in coho salmon (Oncorhynchus kisutch). Fish received OTC (100 mg/kg body weight/day) orally for 2 weeks. The percentage of liver to body weight (hepatosomatic index; HSI) and plasma biochemical parameter, alanine aminotransferase (ALT) activity, of the group fed a diet containing OTC were observed to be significantly higher than those of the control group. The total glutathione (tGSH) levels in the liver of OTC-fed fish were four fold higher than those in control fish and double the control levels in muscle and stomach. Plasma tGSH levels in OTC-fed fish were also higher than those in control fish. Expression levels of heat shock protein 70 in the liver, muscle, and stomach decreased by OTC administration. Accordingly, OTC-induced stress might increase the metabolic turnover of GSH due to consumption by scavenging oxidants generated by stress. These results concerning the changing patterns of stress-related biomarkers indicate that excessive doses of OTC fed to coho salmon induce oxidative stress, which might enhance oxidation in the body and result in damage to tissues, especially in the liver. The present results also suggest that tissue-specific damage caused by OTC might already exist in fish.

Hongsibsong, Surat; Kerdnoi, Tanyaporn; Polyiem, Watcharapon; Srinual, Niphan; Patarasiriwong, Vanvimol; Prapamontol, Tippawan

doi: 10.1007/s11356-015-4916-6pmid: 26111751

Organophosphate and carbamate pesticides have been widely used by farmers for crop protection and pest control. Inhibition of acetylcholinesterase (AChE) in erythrocyte and butyrylcholinesterase (BChE) in plasma is the predominant toxic effect of organophosphate and carbamate pesticides. Mae Taeng District, Chiang Mai Province, is one of the large areas of growing vegetables and fruits. Due to their regular exposure to these pesticides, the farmers are affected by this toxicity. The objective of the study was to examine the AChE and the BChE activity levels in the blood of 102 farmers for comparison of exposure in two cropping seasons, winter and hot. Blood samples were collected in December 2013 (winter) and April–June 2014 (hot). A total of 102 farmers joined the study, represented by 76 males (74.5 %) and 26 females (25.5 %). The age of most of the farmers was 53.4 ± 8.7 years. Out of 102, 21 farmers used carbamate pesticides. The results showed that the AChE and the BChE activity levels of all the farmers were 3.27 ± 0.84 Unit/mL and 2.15 ± 0.58 Unit/mL, respectively. The AChE and the BChE activity levels in males were 3.31 ± 0.88 Unit/mL and 1.97 ± 0.60 U/mL, respectively, during winter and 3.27 ± 0.82 Unit/mL and 2.15 ± 0.58 U/mL, respectively, during the hot season, and AChE and the BChE activity levels in females were 3.27 ± 0.82 U/mL and 2.44 ± 0.56 U/mL, respectively, during the hot season. The cholinesterase activity levels, both AChE and BChE, in the male farmers’ blood had significant difference between the two seasons, while in the case of the female farmers, there was significant difference in the BChE activity levels, at p < 0.05. The BChE activity level was found to significantly correlate with self-spray (p < 0.05), which implies that the BChE activity decreased when they sprayed by themselves. The cholinesterase activity levels of the present study were lower than those of the other studies, which may be an indication of some chronic effect of exposure to anticholinesterase pesticides. Thus, it is recommended that the use of pesticides be decreased, together with increase in the awareness of the impact of pesticides on health; also recommended is regular monitoring of blood cholinesterase.

Hashimoto, Shunji; Zushi, Yasuyuki; Takazawa, Yoshikatsu; Ieda, Teruyo; Fushimi, Akihiro; Tanabe, Kiyoshi; Shibata, Yasuyuki

doi: 10.1007/s11356-015-5059-5pmid: 26194242

Thousands of organohalogen compounds, including hazardous chemicals such as polychlorinated biphenyls (PCBs) and other persistent organic pollutants (POPs), were selectively and simultaneously detected and identified with simple, or no, purification from environmental sample extracts by using several advanced methods. The methods used were software extraction from two-dimensional gas chromatography–high-resolution time-of-flight mass spectrometry (GC × GC–HRTofMS) data, measurement by negative chemical ionization with HRTofMS, and neutral loss scanning (NLS) with GC × GC–MS/MS. Global and selective detection of organochlorines and bromines in environmental samples such as sediments and fly ash was achieved by NLS using GC × GC–MS/MS (QQQ), with the expected losses of 35Cl and 79Br. We confirmed that negative chemical ionization was effective for sensitive and selective ionization of organohalogens, even using GC × GC–HRTofMS. The 2D total ion chromatograms obtained by using negative chemical ionization and selective extraction of organohalogens using original software from data measured by electron impact ionization were very similar; the software thus functioned well to extract organohalogens. Combining measurements made by using these different methods will help to detect organohalogens selectively and globally. However, to compare the data obtained by individual measurements, the retention times of the peaks on the 2D chromatograms need to match.

Chau, H.; Kadokami, K.; Duong, H.; Kong, L.; Nguyen, T.; Nguyen, T.; Ito, Y.

doi: 10.1007/s11356-015-5060-zpmid: 26199005

The rapid increase in the number and volume of chemical substances being used in modern society has been accompanied by a large number of potentially hazardous chemicals being found in environmental samples. In Vietnam, the monitoring of chemical substances is mainly limited to a small number of known pollutants in spite of rapid economic growth and urbanization, and there is an urgent need to examine a large number of chemicals to prevent impacts from expanding environmental pollution. However, it is difficult to analyze a large number of chemicals using existing methods, because they are time consuming and expensive. In the present study, we determined 1153 substances to grasp a pollution picture of microcontaminants in the aquatic environment. To achieve this objective, we have used two comprehensive analytical methods: (1) solid-phase extraction (SPE) and LC-TOF-MS analysis, and (2) SPE and GC-MS analysis. We collected 42 samples from northern (the Red River and Hanoi), central (Hue and Danang), and southern (Ho Chi Minh City and Saigon-Dongnai River) Vietnam. One hundred and sixty-five compounds were detected at least once. The compounds detected most frequently (>40 % samples) at μg/L concentrations were sterols (cholesterol, beta-sitosterol, stigmasterol, coprostanol), phthalates (bis(2-ethylhexyl) phthalate and di-n-butyl phthalate), and pharmaceutical and personal care products (caffeine, metformin). These contaminants were detected at almost the same detection frequency as in developed countries. The results reveal that surface waters in Vietnam, particularly in the center of large cities, are polluted by a large number of organic micropollutants, with households and business activities as the major sources. In addition, risk quotients (MEC/PNEC values) for nonylphenol, sulfamethoxazole, ampicillin, acetaminophen, erythromycin and clarithromycin were higher than 1, which indicates a possibility of adverse effects on aquatic ecosystems.

Phenrat, Tanapon; Schoenfelder, Daniel; Kirschling, Teresa; Tilton, Robert; Lowry, Gregory

doi: 10.1007/s11356-015-5092-4pmid: 26233743

For in situ groundwater remediation, polyelectrolyte-modified nanoscale zerovalent iron particles (NZVIs) have to be delivered into the subsurface, where they degrade pollutants such as trichloroethylene (TCE). The effect of groundwater organic and ionic solutes on TCE dechlorination using polyelectrolyte-modified NZVIs is unexplored, but is required for an effective remediation design. This study evaluates the TCE dechlorination rate and reaction by-products using poly(aspartate) (PAP)-modified and bare NZVIs in groundwater samples from actual TCE-contaminated sites in Florida, South Carolina, and Michigan. The effects of groundwater solutes on short- and intermediate-term dechlorination rates were evaluated. An adsorbed PAP layer on the NZVIs appeared to limit the adverse effect of groundwater solutes on the TCE dechlorination rate in the first TCE dechlorination cycle (short-term effect). Presumably, the pre-adsorption of PAP “trains” and the Donnan potential in the adsorbed PAP layer prevented groundwater solutes from further blocking NZVI reactive sites, which appeared to substantially decrease the TCE dechlorination rate of bare NZVIs. In the second and third TCE dechlorination cycles (intermediate-term effect), TCE dechlorination rates using PAP-modified NZVIs increased substantially (~100 and 200%, respectively, from the rate of the first spike). The desorption of PAP from the surface of NZVIs over time due to salt-induced desorption is hypothesized to restore NZVI reactivity with TCE. This study suggests that NZVI surface modification with small, charged macromolecules, such as PAP, helps to restore NZVI reactivity due to gradual PAP desorption in groundwater.

Mai, Pham; Thuong, Nguyen; Tham, Trinh; Hoang, Nguyen; Anh, Hoang; Tri, Tran; Hung, Le; Nhung, Dao; Nam, Vu; Hue, Nguyen; Huong, Nguyen; Anh, Duong; Minh, Nguyen; Minh, Tu

Babakhani, Peyman; Fagerlund, Fritjof; Shamsai, Abolfazl; Lowry, Gregory; Phenrat, Tanapon

doi: 10.1007/s11356-015-5193-0pmid: 26300356

The solute transport model MODFLOW has become a standard tool in risk assessment and remediation design. However, particle transport models that take into account both particle agglomeration and deposition phenomena are far less developed. The main objective of the present study was to evaluate the feasibility of adapting the standard code MODFLOW/MT3D to simulate the agglomeration and transport of three different types of polymer-modified nanoscale zerovalent iron (NZVI) in one-dimensional (1-D) and two-dimensional (2-D) saturated porous media. A first-order decay of the particle population was used to account for the agglomeration of particles. An iterative technique was used to optimize the model parameters. The model provided good matches to 1-D NZVI-breakthrough data sets, with R 2 values ranging from 0.96 to 0.99, and mass recovery differences between the experimental results and simulations ranged from 0.1 to 1.8 %. Similarly, simulations of NZVI transport in the heterogeneous 2-D model demonstrated that the model can be applied to more complicated heterogeneous domains. However, the fits were less good, with the R 2 values in the 2-D modeling cases ranging from 0.75 to 0.95, while the mass recovery differences ranged from 0.7 to 6.5 %. Nevertheless, the predicted NZVI concentration contours during transport were in good agreement with the 2-D experimental observations. The model provides insights into NZVI transport in porous media by mathematically decoupling agglomeration, attachment, and detachment, and it illustrates the importance of each phenomenon in various situations.

Watanabe, Nobuhisa; Takata, Mitsuyasu; Takemine, Shusuke; Yamamoto, Katsuya

doi: 10.1007/s11356-015-5353-2pmid: 26358211

Waste disposal site is one of the important sinks of chemicals. A significant amount of perfluoroalkyl and polyfluoroalkyl substances (PFASs) such as perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), and perfluorohexanoic acid (PFHxA) have been brought into it. Because of their aqueous solubility, PFASs are released to landfill effluent waters, from which PFASs are efficiently collected by adsorption technique using granular activated carbon (GAC). The exhausted GAC is reactivated by heating processes. The mineralization of PFASs during the reactivation process was studied. Being thermally treated in N2 atmosphere, the recovery rate of mineralized fluorine and PFC homologues including short-chained perfluorocarboxylic acids was determined. If the reagent form of PFOA, PFHxA, and PFOS were treated at 700 °C, the recovery of mineralized fluorine was less than 30, 46, and 72 %, respectively. The rate increased to 51, 74, and 70 %, if PFASs were adsorbed onto GAC in advance; moreover, addition of excess sodium hydroxide (NaOH) improved the recovery to 74, 91, and 90 %. Residual PFAS homologue was less than 1 % of the original amount. Steamed condition did not affect destruction. The significant role of GAC was to suppress volatile release of PFASs from thermal ambient, whereas NaOH enhanced destruction and retained mineralized fluorine on the GAC surface. Comparing the recovery of mineralized fluorine, the degradability of PFOS was considered to be higher than PFOA and PFHxA. Whole mass balance missing 9~26 % of initial amount suggested formation of some volatile organofluoro compounds beyond analytical coverage.