Monitoring of Phthalic Acid Monoesters in River Water by Solid-Phase Extraction and GC-MS Determination

Abstract

An analytical method for monitoring 10 phthalic acid monoesters in river water was investigated by solid-phase extraction, methylation with diazomethane, and GC-MS. Two cartridge-type solid phases packed with octadesyl-coated silica (C18) and styrenedivinyl polymer (PS-2) and one disk-type solid phase made from octadesyl-coated styrenedivinylbenzene polymer (SDB-XD) were investigated in solid-phase extraction. PS-2 gave the highest recoveries of the three solid phases, and recoveries of more than 80% of the monoesters in filtered water samples were obtained at pH 2 to 3 with PS-2 at the spiked level of 0.1 microg L(-1), except for monomethyl-phthalate (MMP), in which more than 72% of the monoesters were recovered. For the monoesters in the suspended solids (SS), an acidic methanol extract of SS was added to purified water acidified to pH 2, and the monoesters were extracted with PS-2. The recoveries of the monoesters in SS were more than 80%, but the recoveries of MMP were more than 57%. The method detection limit (MDL) of each phthalic acid monoester in 500 mL of water sample and in 2 mg of dry weight of SS ranged from 0.010 to 0.030 microg L(-1) and from 1 to 11 microg g(-1), respectively. Monitoring of phthalic acid monoesters in the Tama River in Tokyo was conducted every month from March 1999 to February 2000 using the present method. MMP, mono-n-butyl-phthalate (MBP), and mono-(2-ethylhexyl)-phthalate (MEHP) were detected at concentrations of 0.030-0.0340, 0.010-0.480, and 0.010-1.30 microg L(-1), respectively, in the filtered water samples but were not detected in SS. Dimethyl-phthalate (DMP), di-n-butyl-phthalate (DBP), and di-(2-ethylhexyl)-phthalate (DEHP) were detected in the river water at concentrations of 0.010-0.092, 0.008-0.540, and 0.013-3.60 microg L(-1), respectively. Diethyl-, di-iso-butyl-, and benzylbutyl-phthalates were also detected at concentrations of nanograms per liter, whereas the corresponding monoesters did not appear. The concentrations of MBP and MEHP in the river water were slightly lower than those of the corresponding diesters at the majority of sampling sites and sampling times.

Estimation of Estrogenic and Anti-estrogenic Activities of Some Phthalate Diesters and Monoesters by MCF-7 Cell Proliferation Assay in Vitro

“…7a-[9-(4,4,5,5,5-Pentafluoropentylsulfinyl)nonyl]estra-1,3,5(10)-triene-3,17b-diol (ICI 182,780) was from Tocris Cookson, Ltd. DEP, di-npropyl phthalate (DPrP), DBP, di-n-hexyl phthalate (DHP), DCHP, DEHP, and BBP were from Aldrich. Di-n-pentyl phthalate (DPP) was from Wako Pure Chemical Industries, Ltd. All the phthalate monoesters: MMP, monoethyl phthalate (MEP), mono-n-propyl phthalate (MPrP), monoisopropyl phthalate (MIPrP), MBP, monoisobutyl phthalate (MIBP), mono-n-pentyl phthalate (MPP), monocyclohexyl phthalate (MCHP), monobenzyl phthalate (MBZP), mono-n-octyl phthalate (MOP) and MEHP were synthesized 3) by the method of Snell,26) and their purities were 94.7 to 99.4%. Cell Culture and Proliferation Assay Human breast cancer estrogen-sensitive MCF-7 cells were a generous gift from Drs.…”

Transesterification in the Microbial Degradation of Phthalate Esters

“…Therefore, PEs are widely distributed in the atmosphere 14) and hydrosphere. [15][16][17] In our previous study, we measured the concentrations (0.1-10 µg/l) of dEHP and dibutyl phthalate (dBP, the second-most abundant PE) in several water samples (river water, tap water, well water, and mineral water). 15) In the Tama River, Tokyo, Japan, the concentrations of dEHP and dBP were found to be 0.013-3.60 and 0.010-0.54 µg/l, respectively; moreover, the concentrations were higher in the downstream areas than in upstream areas.…”

“…15) In the Tama River, Tokyo, Japan, the concentrations of dEHP and dBP were found to be 0.013-3.60 and 0.010-0.54 µg/l, respectively; moreover, the concentrations were higher in the downstream areas than in upstream areas. 17) Biodegradation of PEs involves the sequential hydrolysis of each ester-alkyl chain, which is accompanied by the formation of phthalic acid and certain monoesters. 18) However, it is uncertain whether additional transformation products contribute to the toxicity of PEs.…”

A Mono-2-Ethylhexyl Phthalate Hydrolase from a Gordonia sp. That Is Able To Dissimilate Di-2-Ethylhexyl Phthalate

“…These compounds arise from domestic and industrial wastewater because PAEs easily leak from plastic goods, such as tableware, and might be discharged from plastic-producing plants. PAEs are recalcitrant compounds and have accumulated as environmental contaminants, and they have been detected in the water and sediments of rivers, seas, and lakes at many points around the world (10,28,35). PAEs are suspected to be endocrine-disrupting chemicals (5,13,16,32,37).…”