Ryota Shinohara

Plant Uptake of Pharmaceutical Chemicals Detected in Recycled Organic Manure and Reclaimed Wastewater

Land application of recycled manure produced from biosolids and reclaimed wastewater can transfer pharmaceutical chemicals to terrestrial environments, giving rise to potential accumulation of these residues in edible plants. In this study, the potential for plant uptake of 13 pharmaceutical chemicals, and the relation between the accumulation features within the plant and the physicochemical properties were examined by exposing pea and cucumber to an aqueous solution containing pharmaceutical chemicals. Ten of 13 compounds tested were detected in plant leaves and stems. Comparison of the plant uptake characteristics and the octanol-water partition coefficient of pharmaceutical chemicals showed that compounds with an intermediate polarity such as carbamazepine and crotamiton could be easily transported to plant shoots. Moreover, these results suggest the possibility of highly hydrophilic pharmaceutical chemicals such as trimethoprim and sulfonamides to be accumulated in plant roots owing to their low permeability in root cell membranes.

Determination of trialkyl and triaryl phosphates in environmental samples

Abstract Analytical methods of trialkyl and triaryl phosphate esters in water and sediment were developed. An environmental survey of them was performed using developed methods. The extract with dichloromethane (water sample) or acetone (sediment sample) was analyzed with a gas chromatograph equipped with a flame photometric detector and a gas chromatograph/mass spectrometer after clean-up through Florisil column. The separation of gas chromatography was good with 2% OV-17 + 2% PZ-179 on Uniport HPS. Recoveries fortified with 0.3–3 μg were 71–98% for water sample and 78–95% for sediment sample. In the environmental survey, tributyl phosphate (5–36 ng l −1 ), Tris (3-chloropropyl) phosphate (16–176 ng l −1 ), Tris (2-chloroethyl) phosphate (TCEP) (14–347 ng l −1 ), Tris (2,3-dichloropropyl) phosphate (CRP) (23–136 ng l −1 ), triphenyl phosphate (13–31 ng l −1 ), and tricresyl phosphate (67–259 ng l −1 ) were detected in river water and seawater, and TCEP (13-28 ng g −1 ) and CRP (9–17 ng g −1 ) were detected in sediment.

Determination of primary and secondary aliphatic amines in the environment as sulphonamide derivatives by gas chromatography−mass spectrometry

Abstract A gas chromatographic—mass spectrometric (GCMS) method for the determination of primary and secondary aliphatic amines in water and sediment was developed. A standard of amines was added to river water, sea water and sea sediment, and distilled under alkaline conditions. The distillate was reacted with benzenesulphonyl chloride to form the corresponding sulphonamides. After extracting the derivatives into dichloromethane, the organic layer was concentrated to a definite volume. The determination was carried out by GCMS with selected-ion monitoring. The detection limits of amines in water and sediment were 0.02–2 μg/1 and 0.5–50 μg/kg, respectively. The recoveries were 68.4–98.8%.

Uptake and Tissue Distribution of Pharmaceuticals and Personal Care Products in Wild Fish from Treated-wastewater Impacted Streams

A fish plasma model (FPM) has been proposed as a screening technique to prioritize potential hazardous pharmaceuticals to wild fish. However, this approach does not account for inter- or intraspecies variability of pharmacokinetic and pharmacodynamic parameters. The present study elucidated the uptake potency (from ambient water), tissue distribution, and biological risk of 20 pharmaceutical and personal care product (PPCP) residues in wild cyprinoid fish inhabiting treated-wastewater-impacted streams. In order to clarify the uncertainty of the FPM for PPCPs, we compared the plasma bioaccumulation factor in the field (BAFplasma = measured fish plasma/ambient water concentration ratio) with the predicted plasma bioconcentration factor (BCFplasma = fish plasma predicted by use of theoretical partition coefficients/ambient water concentration ratio) in the actual environment. As a result, the measured maximum BAFplasma of inflammatory agents was up to 17 times higher than theoretical BCFplasma values, leading to possible underestimation of toxicological risk on wild fish. When the tissue-blood partition coefficients (tissue/blood concentration ratios) of PPCPs were estimated, higher transportability into tissues, especially the brain, was found for psychotropic agents, but brain/plasma ratios widely varied among individual fish (up to 28-fold). In the present study, we provide a valuable data set on the intraspecies variability of PPCP pharmacokinetics, and our results emphasize the importance of determining PPCP concentrations in possible target organs as well as in the blood to assess the risk of PPCPs on wild fish.

Simultaneous determination of polar pharmaceuticals and personal care products in biological organs and tissues.

In the present study, a sensitive and accurate isotope dilution method was developed for the simultaneous determination of 17 polar pharmaceutical and personal care product (PPCP) residues (logKow=1.40-5.74), including 14 pharmaceuticals and 3 personal care products, in biological organs and tissues. The proposed method involved enzymatic hydrolysis, followed by sequential clean-up using silica gel chromatography and gel permeation chromatography, and analysis via ultra-high-performance liquid chromatography with tandem mass spectrometry. This method yielded acceptable absolute recoveries (48-88%) and internal standard-corrected recoveries (90-130%) for 17 PPCPs. Method detection limits were between 0.0092 and 3.2ngg(-1) wet weight, and the limits of quantification were between 0.020 and 8.7ngg(-1) wet weight. The method can be used to readily detect the target compounds at trace levels while minimizing the required sample volume. The developed method was applied to the determination of 17 PPCPs in the liver and kidney of 17 birds collected from Japan and also in the plasma, liver, and brain of 7 cyprinoid fish from an effluent-dominated stream in Japan. Triclosan was detected in 5 of 11 fish-eating birds but not in non-fish-eating birds, suggesting the contamination of prey fish by the chemical. Non-steroidal anti-inflammatory drugs, antibacterial agents, and psychotropic agents were frequently detected in the fish tissues. In addition, 7 of the target compounds were found in fish brain. The median brain/plasma ratios of the psychotropic agents ranged from 1.6 (carbamazepine) to 12 (diphenhydramine), indicating high transportability to fish brain.

Residues of pharmaceutical products in recycled organic manure produced from sewage sludge and solid waste from livestock and relationship to their fermentation level

In recent years, sludge generated in sewage treatment plants (STPs) and solid waste from livestock being utilized is useful for circulation of nourishment in farmlands as recycled organic manure (ROM). In this study, we determined the residue levels and patterns of 12 pharmaceutical products generated by human activity in the ROMs produced from human waste sludge (HWS), sewage sludge (SS), cattle manure (CM), poultry manure (PM), swine manure (SM) and horse manure (HM). The kind and number of pharmaceutical products detected in ROMs were different. Fluoroquinolones (FQs) were detected at high levels in HWS and SS samples. In addition, the detection frequency and concentration levels of sulfonamides (SAs) in PM and SM were high. Moreover, high concentrations of chlortetracycline (CTC) were found in only SM. These differences reflect specific adherence adsorption of the pharmaceutical products to different livestock and humans. Moreover, it was found that the concentrations of pharmaceutical products and fermentation levels of ROMs had significant positive correlation (r=0.41, p=0.024). When the fermentation test of ROM was conducted in a rotary fermentor in a lab scale test, the residue levels of pharmaceutical products decreased effectively except carbamazepine (CBZ). The rates of decrease were in the case of tetracyclines (TCs): 85-92%, FQs: 81-100%, erythromycine: 67%, SAs: 79-95%, trimethoprim: 86% and CBZ: 37% by 30 d. Pharmaceutical products that can be decomposed by fermentation process at the lowest impact of residual antibiotic activities may therefore be considered as environmentally friendly medicines.

Determination of trace azaarenes in water by gas chromatography and gas chromatography—mass spectrometry

Abstract The method in which trace two-, three- and five-ring azaarenes in water samples can be determined was investigated by gas chromatography (GC). The trace azaarenes in water were concentrated with an Amberlite XAD-2 resin column and separated into azaarenes with two and three rings and those with five rings by a solvent extraction, followed by a clean-up procedure using an alumina column. The azaarenes thereby separated were determined by GC with a flame thermionic detector (GC—FTD) and GC—mass spectrometry with a selected ion monitor detector (GC—MS—SIM). Detection limits of the azaarenes by GC—FTD were in the range 0.5–3 ng and those of GC—MS—SIM in the range 0.02–0.5 ng. Utilization of GC-MS-SIM was very useful for the determination of trace azaarenes in environmental samples.

Behavior of Pharmaceuticals in Waste Water Treatment Plant in Japan

The fate of pharmaceuticals in a wastewater treatment plant (WWTP) in Kumamoto, Japan with activated sludge treatment is reported. Selected pharmaceuticals were detected in influent. Results from the present study confirmed that Acetaminophen, Amoxicillin, Ampicillin and Famotidine were removed at a high rate (>90% efficiency). In contrast, removal efficiency of Ketoprofen, Losartan, Oseltamivir, Carbamazepine, and Diclofenac was relatively low (<50%). The selected pharmaceuticals were also detected in raw sludge. In digestive process, Indomethacin, Atenolol, Famotidine, Trimethoprim and Cyclofosamide were removed at a high (>70% efficiency). On the other hand, removal of Carbamazepine, Ketoprofen and Diclofenac was not efficient (<50%).

Identification and determination of trace organic substances in tap water by computerized gas chromatography-mass spectrometry and mass fragmentography

Abstract Tap water was examined for the presence of trace organic substances by using the Amberlite XAD-2 resin adsorption method, computerized gas chromatography-mass spectrometry, high resolution mass spectrometry, and mass fragmentography. Chemical ionization and field desorption mass spectrometry were used for the analysis of high polar compounds. By these methods, a large number of alkylbenzenes, odorous components (menthol, acetophenone and its derivatives, and benzaldehyde), and several plasticizers (dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di(2-ethylhexyl) phthalate, di(2-ethylhexyl) adiptate, and tributyl phosphate) were found in a concentration of 1–240 parts per thousand million.

Identification of triclosan intermediates produced by oxidative degradation using TiO2 in pure water and their endocrine disrupting activities.

The photodegradation pathways of 2-(2,4-dichlorophenoxy)-5-chlorophenol (triclosan) in water were studied. The main purposes were to identify structures of intermediates derived by radical reaction using TiO2 advanced oxidation processes and to evaluate the endocrine disrupting activities in treated triclosan during oxidative reactions. Intermediates such as dichlorophenols, 2,8-dibenzo-p-dioxin, tetrachlorinated diphenyl ether (tetraclosan) and hydroxylated triclosan were produced by photoreaction. The estrogen, thyroid hormone and retinoid X receptor activities of the treated triclosan were measured with the yeast two-hybrid assay. It was found that tetraclosan and 2,4-dichlorophenol have stronger thyroid hormone activities than triclosan in the presence of S9.