Rapid measurement of Phthalic acid Ester environmental hormones using ion mobility spectrometry

Phthalic acid esters (PAEs) are ubiquitous environmental pollutants and are recognized as a threat to the environment and agricultural product safety across the world. In order to investigate the level of PAEs in garlic, soils, and agricultural films from Pizhou City, Jiangsu province, China, 11 garlic samples, 106 soil samples, and 4 agricultural film samples were collected and analyzed using GC-MS. In addition, the uptake and transport characteristics of six PAEs compounds classified as priority pollutants by the United States Environmental Protection Agency (EPA) in the garlic cultivar Daqingke were investigated under hydroponic conditions. The results indicated that dibutyl phthalate (DBP) and di-(2-ethylhexyl) phthalate (DEHP) were the dominant PAEs species in garlic cloves of the different garlic varieties from Pizhou City. The average contents of DBP and DEHP in garlic cloves were 0.611 mg·kg-1 and 0.167 mg·kg-1, respectively, which were significantly higher than those of the commercial varieties of garlic. The concentrations of DBP and DEHP differed in three tissues of garlic bulbs, ordered as the skin of garlic bulb>skin of garlic clove>garlic clove. Dimethyl phthalate (DMP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), DBP, and DEHP were the main PAEs species and were detected in all the surface soils collected from Pizhou City. Compared with the soil allowable concentrations of the six PAEs in the United States, the DMP and DBP concentrations in approximately 100% and 63.2% of soil samples exceeded the recommended allowable concentrations set by the EPA. However, the levels of DEP, DIBP, and DEHP in the soils were below the maximum allowable concentrations set by the EPA. Nevertheless, the average content of DEHP in soils was 486 μg·kg-1 and was found to be much higher than that in the other four PAEs. Six PAEs, including DMP, DEP, DIBP, DBP, butyl benzyl phthalate (BBP), and DEHP, were detected in all the agricultural film samples. Among them, the contents of DBP and DEHP in the agricultural films were the highest, accounting for 53.7%-63.2% of the total PAEs. The amount of PAEs present in the residual film was significantly lower than that in the new film, and all six PAEs were detected in garlic or soil samples, suggesting that agricultural film can be an important source of PAEs in garlic farming soils and garlic. Furthermore, the garlic plants absorbed DMP and DEP efficiently from the substrate and showed higher translocation factors (TFs) for DMP and DEP than those for DBP, BBP, DEHP, and di-n-octyl phthalate (DnOP), resulting in a higher accumulation of DMP and DEP in the over-ground parts of garlic. In contrast, DBP and BBP in roots of garlic displayed higher bioconcentration factors (57.4 and 81.5, respectively) compared to those of the other four PAEs, whereas the TFs of DBP and BBP were lower; this may have contributed to the high accumulation of DBP in garlic bulbs. The BCFs and TFs of DEHP and DnOP in garlic were relatively lower, but the DEHP had been detected in all garlic cloves, which may be a result of the higher DEHP contents in soils.

Herein, the catchment-wide temporal dynamics and potential ecotoxicological risk of phthalic acid esters (PAEs) in aquatic ecosystems were assessed. Specifically, water samples were collected for a period of six consecutive months from seven selected sites, i.e., covering both dry and wet seasons for seasonal variabilities. The appraised PAEs comprised dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), benzylbutyl phthalate (BBP), diphenyl phthalate (DPP), di-n-hexyl phthalate (DHP), bis(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate (DOP), diisodecyl phthalate (DiDP) and diisononyl phthalate (DiNP)) in municipal wastewater effluents, rivers and dam. Their concentrations were quantified using a gas chromatography–flame ionisation detector (GC–FID) via the liquid–liquid extraction mode. The appraised PAEs were ubiquitous in the selected sampling points, with DBP being the most abundant PAE homologue throughout the assessed localities. In particular, quantifiable concentrations were 18.9, 37.9 and 11.5 μg/L for DBP in wastewater effluents, rivers and the dam catchment, respectively, and for overall Σ10PAEs of minimum, mean and maximum of 0.492, 3.6 ± 9.82 and 63.2 μg/L, respectively. In addition, PAE concentrations in the effluents, rivers, and dam samples showed no significant differences with p < 0.05. The overall prominent sequence for ∑PAEs registered: 53.3 > 10.1 > 10.0 > 9.8 > 4.3 > 2.5 > 1.8 > 1.7 > 1.1 > 0.9% for DBP > DEHP > DiDP > DOP > DHP > DPP > BBP > DMP > DEP > DiNP, respectively. The ecotoxicological risk assessment (risk quotient method) showed that DBP and DiDP posed high risk (RQ ≥ 1), and DOP, DEHP, DHP, DiNP and BBP posed median risk to aquatic organisms (0.1 ≤ RQ < 1), while the risk from DMP and DEP was minimal (RQ < 0.1). Additionally, DBP, DEHP, DOP, DPP and DiDP were higher than the water criterion (3 μg/L) of PAEs recommended by the United States Environmental Protection Agency (USEPA) for the protection of aquatic life. Findings from this study should go a long way in guiding regulators, custodians and catchment management forums, along with interested and affected parties, regarding the status and potential ecotoxicological effects of PAEs in the receiving environment.

Accumulation and transport patterns of six phthalic acid esters (PAEs) in two leafy vegetables under hydroponic conditions

Whole-cell biocatalysis for phthalate esters biodegradation in wastewater by a saline soil bacteria SSB-consortium

Occurrence, bioaccumulation, and partitioning of phthalate acid esters in the third largest freshwater lake (Lake Taihu) in China

Phthalates are esters of phthalic acid used industrially as plastic additives, however, these are not covalently bound to the polymer matrix and therefore can be released to the environment. The aim of this study was to evaluate the effect of four phthalates: dibutyl phthalate (DBP), benzyl butyl phthalate (BBP), diethyl phthalate (DEP) and diethylhexyl phthalate (DEHP) on the in vitro expansion of human hematopoietic cells from umbilical cord blood. For this, 0.5 × 106 cells/mL were exposure to concentrations ranging from 0.1 to 100μg/mL and the total cell expansion was determined after 14days of culture in IMDM-cytokines medium. The control cultures attained 1.31 ± 0.21 × 106 cell/mL, whereas the cultures exposed to DBP, BBP and DEHP showed a reduction from 23 to 81%, 17 to 69% and 15 to 93.5%, respectively. DEP did not affect the total cell expansion. The most significant decrease on total cell expansion was observed at 0.1μg/mL DBP, 100μg/mL BBP and 10μg/mL DEHP (p < 0.05). Additionally, the effect of these compounds on the expansion of hematopoietic progenitors was analyzed by clonogenic assays as colony forming units (CFU). The CFU decreased considerably compared with respect to the control cultures. The reduction was 74.6 and 99.1% at 10 and 100μg/mL DBP respectively, whereas 100μg/mL BBP and 100μg/mL DEHP reduced the CFU expansion in 97.1% and 81%, respectively. Cultures exposed to DEP did not show significant differences. The results demonstrate the toxicity of DBP, BBP and DEHP on the human hematopoietic stem cells.

In this study, the levels of six PAEs [bis (2-ethylhexyl) phthalate (DEHP), butyl benzyl phthalate (BBP), dibutyl phthalate (DBP), diethyl phthalate (DEP), dimethyl phthalate (DMP) and di-n-octyl phthalate (DNOP)] were determined from four types of bottled water)non-carbonated, mineral, carbonated and carbonated flavoured) using MSPE method (magnetic solid phase extraction) and GC/MS technique (gas chromatography/mass spectrometry). The mean concentration of total PAEs was 6.11 ± 1.43 µg/L. The mean concentration of DEHP was 2.22 ± 0.76 µg/L and was lower than the United States Environmental Protection Agency (USEPA) standard level in drinking water (6 μg/L for DEHP). The highest mean level of total PAE was observed in carbonated water (7.43 ± 2.03 μg/L) and the lowest mean level of total PAE was observed in non-carbonated water (5.15 ± 0.41 μg/L). The Monte Carlo method was applied to calculate the Target Hazard Quotient (THQ), Chronic Daily Intake (CDI), and Incremental Life Cancer Risk (ILCR) indexes. In all samples, the rank order of the estimated THQ values based on the 95% percentile was DEHP (4.77E-4) > DBP (2.25E-5) > BBP (1.99E-5) > DEP (2.75E-6) and there would be unlikely non-carcinogenic risks for consumers (THQ<1). The incremental lifetime cancer risk assessment revealed that phthalate esters (DEHP) in evaluated bottled water samples did not pose a serious concern to humans.

Phthalate esters and plastic debris abundance in the Red Sea and Sharm Obhur and their ecological risk level

Biodegradation of four phthalate esters in sludge

Occurrence of phthalic acid esters in source waters: a nationwide survey in China during the period of 2009–2012

Simultaneous GC-MS determination of eight phthalates in total and migrated portions of plasticized polymeric toys and childcare articles.

Exxon Chemical as exclusive distributor of ICI speciality plasticizers

Removal of six phthalic acid esters (PAEs) from domestic sewage by constructed wetlands

Diethyl phthalate (DEP) and dimethyl phthalate (DMP), phthalic acid ester (PAE) plasticizers, were evaluated for developmental toxicity because of reports in the literature that some PAE were embryotoxic and teratogenic. A previous study (Singh et al., '72) suggested that an increased incidence of skeletal defects in rats might result from gestational exposure to DEP (0.6-1.9 g/kg) or DMP (0.4-1.3 g/kg), ip, on gestational days (gd) 5, 10, and 15. In the current study DEP (0, 0.25, 2.5, and 5%) or DMP (0, 0.25, 1, and 5%) in feed (approximately 0.2-4.0 g/kg/day) were supplied to timed-mated rats from gd 6 to 15. Treatment with 5% DMP resulted in increased relative maternal liver weight. Also, animals exhibited reduced body weight gain during treatment (5% DEP or DMP) and during gestation (5% DEP). Weight gain corrected for gravid uterine weight was also reduced in animals fed 5% DEP. However, high-dose treatment with either DEP or DMP resulted in changes in food and water consumption paralleling the body weight reductions, suggesting that apparent toxic effects on maternal body weight may reflect PAE/feed unpalatability. Treatment with 2.5% DEP resulted in only transient changes in body weight during early treatment. The only maternal effects at 0.25 or 1% DMP were minor changes in food and/or water consumption, and there were no effects at 0.25% DEP. Thus, the NOAELs for maternal toxicity were 1% DMP and 0.25% DEP. In contrast to the observed maternal toxicity, there was no effect of DEP or DMP treatment on any parameter of embryo/fetal development, except an increased incidence of supernumerary ribs (a variation) in the 5% DEP group. These results do not support the conclusion of other investigators that DEP and DMP are potent developmental toxicants. Rather, they suggest that the short-chain PAE are less developmentally toxic than PAE with more complex substitution groups, e.g., di(2-ethylhexyl) phthalate, mono(2-ethylhexyl) phthalate, and butyl benzyl phthalate.

Phthalic acid esters (PAEs) have a negative impact on living organisms in the environment, therefore, are among the group of Endocrine Disrupting Compounds (ECDs). Unfortunately, conventional methods used in municipal wastewater treatment plants (MWWTPs) are not designed to eliminate PAEs. For this reason, the development of cheap and simple but very effective techniques for the removal of such residues from wastewater is crucial. The main aim of this study was the evaluation of the removal of six selected PAEs: diethyl phthalate (DEP), di-n-octyl phthalate (DOP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), bis(2-ethylhexyl) phthalate (DEHP) and dimethyl phthalate (DMP), in real MWWTPs supported by constructed wetlands (MWWTP–CW system). For the first time, the possibility of using three new plants for this purpose, Cyperus papyrus (papyrus), Lysimachia nemorum (yellow pimpernel) and Euonymus europaeus (European spindle), has been presented. For determining the target PAEs in wastewater samples, a method of SPE (Solid-Phase Extraction)–GC–MS(SIM) was developed and validated, and for plant materials, a method of UAE (Ultrasound-Assisted Extraction)–SPE–GC–MS(SIM) was proposed. The obtained data showed that the application of the MWWTP–CW system allows a significant increase in the removal of DEP, DBP, BBP and DEHP from the wastewater stream. Euonymus europaeus was the most effective among the tested plant species for the uptake of analytes (8938 ng × g−1 dry weight), thus, this plant was found to be optimal for supporting conventional MWWTPs.