Di-n-octyl Phthalate Research Articles

Determination of selected dichloroanilines and phthalates in lyophilised mussels samples with ultra-high performance liquid chromatography-tandem mass spectrometry after QuEChERS clean-up

ABSTRACT Mussels, a marine filter organism, constitute a food product and an established sentinel organism for marine pollution. An analytical method following a QuEChERS extraction and clean-up protocol has been developed for the determination of phthalic acid esters (PAE), including di-n-octyl phthalate (DnOP), di-(2-ethyl hexyl) phthalate (DEHP), butyl benzyl phthalate (BBP), di-methyl phthalate (DMP) and di-n-butyl phthalate (DnBP), as well as 3,4-dichloroaniline and 3,5-dichloroaniline in lyophilised mussels samples. A gradient elution program starting from 40% A (methanol-0.1% formic acid) – 60% B (H2O-0.1% formic acid) up to 100% A was applied, with a total duration of 15 min, at a flow rate of 200 μL min−1 using a 1.8 μm particle size C18 analytical column. All target analytes were detected with a triple quadrupole MS, using electrospray ionisation (ESI) in positive ionisation mode, in SRM mode under optimised conditions. Sample preparation consisted of lyophilisation of the mussels sample and grinding, followed by a QuEChERS (Quick, Easy, Cheap, Effective, Rugged, Safe) protocol. Among the different dispersants evaluated for sample clean-up effectiveness, primary secondary amine (PSA) was found to be the most efficient. Results indicated good chromatographic separation, fast sample preparation procedure, low LODs and LOQs, good trueness expressed as recovery and good precision as evaluated by RSD. In the mussels samples examined DEHP was the most abundant PAE, reaching a maximal concentration of 280 μg/kg of lyophilised weight whereas the levels of DnBP were at approximately 36% of the legal migration limit in foods determined by the EU.

Indoor phthalate concentrations in residences in Shihezi, China: implications for preschool children's exposure and risk assessment.

Despite the risks associated with phthalate exposure, there are few studies emphasizing preschool children's exposure to phthalates in residences in Northwest China. In this study, seven phthalates from indoor dust samples were measured in 50 residences in Shihezi, China. Preschool children's exposure doses via non-dietary intake were calculated by Monte Carlo simulation. Risk assessment was conducted by comparing the simulated exposure dose with benchmarks for reproductive toxicity and cancer specified in Proposition 65 of California. The detection frequencies for all selected phthalates were more than 75%, with the exception of benzyl butyl phthalate (BBP) and di-n-octyl phthalate (DNOP). Bis(2-ethylhexyl) phthalate (DEHP) was the most principal compound in the dust samples (median = 455 μg/g and 462 μg/g in the bedroom and living room, respectively). The simulation displayed that the median DBP daily intake was 1.5-1.9 μg/day/kg for preschool children in Shihezi, which was considered a high level compared with similar studies around the world. The risk assessment indicated that almost all preschool children face potential reproductive risk due to dibutyl phthalate (DBP) exposure, with medians of hazard index (HI) from 9.6 to 12.4 for all age groups. Therefore, from a children's health perspective, attention should be paid to reducing indoor phthalate pollution and exposure in this area.

Health risk of phthalates in water environment: Occurrence in water resources, bottled water, and tap water, and burden of disease from exposure through drinking water in tehran, Iran

Occurrence of phthalates in water resources, bottled water, and tap water, and health risk of exposure to the phthalates through drinking water in Tehran, Iran, 2018 were studied. The six phthalates with the most health and environmental concerns, including di-(2-ethylhexyl) phthalate (DEHP), butyl benzyl phthalate (BBP), di-n-butyl phthalate (DBP), diethyl phthalate (DEP), dimethyl phthalate (DMP), and di-n-octyl phthalate (DNOP) were monitored in drinking water and water resources. The average levels (±standard deviation: SD) of the total phthalates in drinking water from the water distribution system, bottled water, surface waters, and ground waters were determined to be 0.76 ± 0.19, 0.96 ± 0.10, 1.06 ± 0.23, and 0.77 ± 0.06 μg/L, respectively. The dominant compounds in the phthalates were DMP and DEHP causing a contribution to the total phthalate levels higher than 60% in all the water sources. The phthalate levels of drinking water significantly increased by contact of hot water with disposable plastic and paper cups and by sunlight exposure of bottled water (p value < 0.05). The hazard quotients (HQs) of DEHP, BBP, DBP, and DEP for all ages both sexes combined were determined to be 1.56 × 10−4, 1.01 × 10−5, 1.80 × 10−5, and 1.29 × 10−6, respectively that were much lower than the boundary value of 1.0. The disability-adjusted life years (DALYs) and DALY rate (per 100,000 people) attributable to DEHP intake through drinking water for all ages both sexes combined were estimated to be 6.385 (uncertainty interval: UI 95% 1.892 to 22.133), and 0.073 (0.022–0.255), respectively. The proportion of mortality in the attributable DALYs was over 96%. The attributable DALY rate exhibited no significant difference by sex, but was considerably affected by age in a manner that the DALY rates ranged from 0.052 (0.015–0.175) in the age group 65 y plus to 0.099 (0.026–0.304) in the age group 5 to 9 y. Both the carcinogenic and non-carcinogenic health risks of the phthalates in drinking water were considered to be very low. The results can also be of importance in terms of developing frameworks to expand the domain of burden of disease study to the other environmental risks.

HYBRID MAGNETIC NANOPARTICLE-FUNCTIONALIZED POLYTHIOPHENES AND ITS POTENTIAL AS A SORBENT TO EXTRACT PHTHALATES

Magnetic polythiophene and poly-3-hexylthiophene was successfully synthesized. FTIR data suggested the presence of functionalized polythiophenes in the nanocomposites. XRD peaks confirmed the entire characteristic peak for Fe3O4 presence in all prepared nanocomposites. From the vibrating sample magnetometry hysterisis loop P3Th-coated MNPs (MNP@P3Th) established great magnetization than other nanocomposites. BET results showed decreasing trend of pore size due to addition of polymer coating. The thermograms of nanocomposite indicated that all the nanocomposites were stable up to 210 °C. The synthesized material was screened for the extraction of commercially available phthalates namely din-octyl phthalate (DNOP) butyl phthalate (DBP), and butyl benzyl phthalate (BBP) and P3Th-coated MNPs (MNP@P3Th) showed highest extraction concentration for all tested phthalates.&#x0D; Keywords: Functionalized polythiophene; Fe3O4 magnetic nanoparticles, phthalates

Urban Watercourses in Peril: Implications of Phthalic Acid Esters on Aquatic Ecosystems Caused by Urban Sprawl

Urban sprawl worldwide warrants the use of large quantities of industrial and household products containing phthalic acid esters (PAEs) resulting in adverse impacts on the quality of aquatic life in urban watercourses. The presence of six PAEs (dimethyl phthalate (DMP), diethyl phthalate (DEP), di(n-butyl) phthalate (DBP), benzyl butyl phthalate (BBP), bis(2-ethylhexyl) phthalate (DEHP), and di(n-octyl) phthalate (DnOP)) in 22 shallow urban watercourses in Colombo and suburbs of Sri Lanka was investigated. The average concentrations of DEP, DBP, BBP, and DEHP in all watercourses varied between 2.5–265.0, 1.0–32.0, 61–108, and 12–165 µg/L, respectively. DMP and DnOP were below the limits of quantification (DMP-0.5 µg/L, DnOP-1.0 µg/L) for all watercourses. DEHP was the most abundant PAE in many watercourses. The significant factors affecting the ubiquitous presence of PAEs in watercourses are the inherent properties of each PAE, presence of industrial and household products with great potential for the migration of PAEs in the sub-catchments, and quality of the receiving water. The contamination levels of PAEs in most of the watercourses are alarmingly high, as evidenced by higher concentrations of DEHP and DBP than those of Canadian permissible levels for the protection of aquatic life (16 and 19 µg/L). This study was the first effort in Sri Lanka to investigate the presence of PAEs in urban watercourses.

Comparative analysis of endocrine disrupting effects of major phthalates in employed two cell lines (MVLN and H295R) and embryonic zebrafish assay

Endocrine disruption potentials of phthalates have been widely recognized, but relatively little is known about relative potency of major phthalates. In the present study, six phthalates were chosen, i.e., dimethyl phthalate (DMP), diethyl phthalate (DEP), di(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate (DnOP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP), and their endocrine disruption effects were evaluated by employing two cell lines and an embryonic zebrafish assay. Binding affinity with estrogen receptors (ERs) and effects on steroidogenesis were evaluated with MVLN and H295R cell assays, respectively. In zebrafish embryos, transcription of genes regulating steroid hormone balance and estrogen receptors was measured. Exposure to DMP, DEP, DEHP, and DnOP significantly increased E2/T ratio in H295R cells. However, no significant binding affinity to ERs was observed in MLVN cells. Exposure to DEHP influenced the expression of vtg1, esr1, and cyp19a1b genes in zebrafish larvae. DMP, DEP, DINP, and DIDP exposure led to significant transcriptional changes even at lower exposure concentrations, suggesting their greater endocrine disruption potency than DEHP in zebrafish. Our findings demonstrate that endocrine disruption upon phthalate exposure varies between in vitro and in vivo assay, and a battery of tests are warranted to understand endocrine disruption potentials of phthalates. Consequences of long-term exposure to phthalates other than DEHP warrant further evaluations.

Exposure and ecological risk of phthalate esters in the Taihu Lake basin, China

The environmental spatial distribution and exposure risk of 6 phthalate esters (PAEs) including dimethyl phthalate (DMP), diethyl phthalate (DEP), butyl benzyl phthalate (BBP), di-n-octyl phthalate (DnOP), bis(2-ethylhexyl) phthalate (DEHP), and dibutyl phthalate (DBP), in surface water and sediment of Taihu Lake basin, China, were investigated at 65 sites. The exposure concentrations of 6 PAEs (∑6PAEs) detected in the samples spanned a range of 0.740–13.0 μg/L in surface water and 5.15–20.9 mg/kg in sediment. DBP and DEHP were the predominant compounds in surface water, with mean concentrations of 1.59 μg/L and 1.29 μg/L, respectively. DnOP was the predominant compound in sediment with mean concentration of 7.41 mg/kg. Ecological risk assessment was conducted by the hazard quotient method in which the predicted no effect concentration (PNEC) was derived from the species sensitivity distribution (SSD) curve. The results showed that DEHP in water phase posed a higher environmental risk than the other PAEs, while the DEP in sediment posed a high risk to the aquatic system. The study contributed to better understanding the presence of PAEs in Taihu Lake basin and provided valuable information for managing and controlling PAEs pollution.

Validated Method for the Detection of Three Phthalates Derived from Marine Invertebrates

This study represents, detailly, the validated method for the extraction and quantification of widespread phthalic acid esters (PAEs) bis(2-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DBP) and di-n-octyl phthalate (DnOP) from solitary ascidians collected from a marine environment. The extraction was based on a pressurized liquid extraction method, using n-hexane as the solvent to extract the target PAEs from dry biological tissues, and was performed in an accelerated solvent extraction instrument. The average recovery of 89.2% was obtained from samples subjected to a pressure of ~1500 psi and 120°C in two 10-min cycles. GC-MS was used for quantification, conducted in single-ion monitoring mode. Following careful and rigorous cleanup procedures to prevent cross-contamination from laboratory glassware, PAE standards showed signals with good specificity. The obtained limits of detection were 130, 122 and 89 ng/g for DEHP, DBP and DnOP, respectively. Accordingly, the calculated limits of quantification were 394, 370 and 270 ng/g for DEHP, DBP and DnOP, respectively. The obtained linearity ranged from 5.4 to 269 ng/ml (equivalent to 135 - 6725 ng/g dry weight), with R2 ≥ 0.998. Concentrations in the range of 200 to 9000 and 400 to 5000 ng/g sample dry weight, for DEHP and DBP, respectively, were obtained from the ascidians. No DnOP was detected in any of the samples. These results indicate that the method presented in this study is applicable for detection of low and trace concentrations of the target PAEs in samples collected from a marine organism, which can serve as a bioindicator of plastic contamination.

Simultano određivanje pet ftalata u belim rakijama korišćenjem tečno-tečne ekstrakcije praćene gasnom hromatografijom

The aim of this paper is the development of the method for determination of five phthalates in white spirits. Dimethyl phthalate (DMP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), di-(2-ethylhexyl) phthalate (DEHP) and di-n-octyl phthalate (DOP) were extracted from white spirits by the optimized liquid-liquid extraction (LLE) method. In order to determine the best method for phthalate determination, LLE procedure was optimized by changing the following parameters: the number of extraction repetitions (1-4), the partial removal of ethanol by evaporation from alcoholic samples prior extraction, the type of agitation and the extraction time. Quantification was achieved by gas chromatography-mass spectrometry (GC-MS) with di-n-butyl adipate (DBA) as internal standard. Phthalates were analyzed using a single ion monitoring (SIM) mode and a base ion for each phthalate was chosen (m/z 149 for DBP, BBP, DEHP and DOP and m/z 163 for DMP). The results show that the most effective phthalate extraction with n-hexane as a solvent is achieved with agitation by hand shaking with one-step extraction. Evaporation of ethanol from alcohol drinks provided the increased recovery value for DMP extraction but did not have an impact on the recovery values of DBP, BBP, DEHP and DOP extractions from the samples.

Spatial distribution and mass loading of phthalate esters in wastewater treatment plants in China: An assessment of human exposure

The occurrence and fate of nine phthalate esters (PAEs), including dimethyl phthalate (DMP), diethyl phthalate (DEP), di‑n‑butyl phthalate (DBP), di-isobutyl phthalate (DIBP), benzyl butyl phthalate (BzBP), di (2‑ethylhexyl) phthalate (DEHP), di‑n‑hexyl phthalate (DNHP), dicyclohexyl phthalate (DCHP), and di‑n‑octyl phthalate (DNOP), in sludges collected from 46 wastewater treatment plants (WWTPs) from 22 Chinese provinces were investigated. The nine PAEs were detected in almost all the sludge samples. DEHP was the most abundant congener in all sludge samples, followed by DBP and DIBP. The DEHP concentrations in sludge were in the range of 0.326–67.8 (mean: 14.7) μg/g dry weight (dw), which were at the lower bound or middle of the concentration range of DEHP in sludge globally (0.0200–3514 μg/g dw). Spatial distribution and mass loading of PAEs in WWTPs were investigated. The concentrations of Σ9PAEs in sludges from different provinces were in the order as follows: Jilin (40.2 μg/g dw) > Liaoning (38.9 μg/g dw) > Beijing (30.7 μg/g dw), while the mass loading of ∑9PAEs in sludges were Guangdong (10.1 tons/yr) > Liaoning (9.97 tons/yr) > Shandong (5.59 tons/yr). Our study showed that the geographical distribution of PAEs in sludges was similar to that in indoor dusts found in earlier study, suggesting the existence of a common source for these chemicals in both matrices. Based on the concentrations measured, human exposure to PAEs through sludge application in soil was evaluated and the exposure dose is minor.

Phthalate acid esters (PAEs) accumulation in coastal sediments from regions with different land use configuration along the Persian Gulf

Phthalate acid esters (PAEs) are widely used as plasticizers in various plastic products and have aroused considerable concern over their ubiquitous presence and potentially hazardous effects on the environment. This research provides the first data on PAEs distribution in the sediments of northern part of the Persian Gulf. To determine the concentration of 16 PAEs, 26 samples of sediments were collected from industrial stations (IS), urban stations (US), agricultural stations (AGS), and natural field stations (NS) from Asalouyeh Harbor coasts from Nov 2016 to Jan 2017. The mean values of Ʃ16PAEs in the samples taken from IS, AGS, US, and NS were 78.08, 11.69, 46.56, and 5.180 µg/g, respectively. The results indicated that the mean concentrations of Ʃ16PAEs in the samples taken from IS and AGS areas were significantly higher (p < 0.05) than the ones taken from US and NS areas. The order of PAEs concentrations in sediment samples were as di(2-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DnBP), butylbenzyl phthalate (BBP), and di-n-octyl phthalate (DnOP), respectively. DEHP was detected in all collected samples and the mean ± SD of its concentration in the IS, US, AGS, and NS regions were as 28.15 ± 4.9, 4.040 ± 0.53, 11.58 ± 1.2, and 1.780 ± 0.78 µg/g, respectively. The major sources of PAEs in the sediments collected from the study region were associated with the industrial and agricultural activities. The findings of this study indicated that the sediments of the Asalouyeh coasts are heavily contaminated with PAEs. They have shown potential ecotoxicological effects on the aquatic organisms and benthic. Therefore, more attention should be paid to prediction of the marine ecosystem in this region by the authorities.

Phthalate esters in indoor dust from several regions, China and their implications for human exposure

Phthalate esters (PAEs) have been used in large quantities all over the world for decades, leading to ubiquitous occurrence in the indoor environment. Indoor dust samples were collected from six geographical regions in China (n = 120) and the concentrations, profiles and human exposure to nine prevalent PAEs from dust were investigated in this study. The total concentrations of nine PAEs (Σ9PAEs) varied from 2.31 to 1590 μg/g (mean: 150 μg/g). The highest concentration of Σ9PAEs was found for dusts from the geographical region of Northeast China (mean: 394 μg/g), which was nearly 8 times higher than that of the lowest value for dusts from the Southwest China (52.1 μg/g). The sum concentrations of six priority controlled PAEs, namely dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BzBP), bis (2-ethylhexyl) phthalate (DEHP) and di-n-octyl phthalate (DNOP), in our study (mean: 133 μg/g) were lower than those found in other regions of the world (230–1280 μg/g) reported in earlier studies. DEHP, DBP and di-iso-butyl phthalate (DIBP) were the major congeners found in all dust samples, cumulatively accounting for 98.7% of Σ9PAEs. The daily intake (DI) of PAEs via dust through the routes of ingestion, inhalation and dermal contact was estimated. Comparably, dust ingestion is the major pathway of human exposure to PAEs from dust and the DI values through dust ingestion were 985 ng/kg/day for children and 126 ng/kg/day for adults in China, respectively. The contribution of indoor dust to the total exposure of human to PAEs varied, depending on the type of PAE congeners. Among PAE congeners, DEHP was the predominant contributor, accounting for 3.45% and 2.39% of the estimated total DIs for Chinese children and adults, respectively. This indicates that indoor dust is an important source of human exposure to certain PAE congeners.

Phthalates and organophosphates in settled dust and HVAC filter dust of U.S. low-income homes: Association with season, building characteristics, and childhood asthma

Phthalates and organophosphates are ubiquitous indoor semi-volatile organic contaminants (SVOCs) that have been widely used as plasticizers and flame retardants in consumer products. Although many studies have assessed their levels in house dust, only a few used dust samples captured by filters of building heating, ventilation, and air conditioning (HVAC) systems. HVAC filters collect particles from large volumes of air over a long period of time (potentially known) and thus provide a spatially and temporally integrated concentration. This study measured concentrations of phthalates and organophosphates in HVAC filter dust and settled floor dust collected from low-income homes in Texas, United States, in both the summer and winter seasons. The most frequently detected compounds were benzyl butyl phthalate (BBzP), di-(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate (DnOP), tris (1-chloro-2-propyl) phosphate (TCIPP), triphenyl phosphate (TPHP), and tris (1,3-dichloroisopropyl) phosphate (TDCIPP). The median level of TCIPP in settled dust was 3- to 180-times higher than levels reported in other studies of residential homes. Significantly higher concentrations were observed in HVAC filter dust as compared to settled dust for most of the frequently detected compounds in both seasons, except for several phthalates in the winter. SVOC concentrations in settled dust in winter were generally higher than in summer, while different seasonality patterns were found for HVAC filter dust. Settled dust samples from homes with vinyl flooring contained significantly higher levels of BBzP and DEHP as compared to homes with other types of floor material. The concentration of DEHP and TDCIPP in settled dust also significantly associated with the presence of carpet in homes. Cleaning activities to remove dust from furniture actually increased the levels of certain compounds in HVAC filter dust, while frequent vacuuming of carpet helped to decrease the concentrations of some compounds in settled dust. Additionally, the size and age of a given house also correlated with the levels of some pollutants in dust. A statistically significant association between DEHP concentration in HVAC filter dust in summer and the severity of asthma in children was observed. These results suggest that HVAC filter dust represents a useful sampling medium to monitor indoor SVOC concentrations with high sensitivity; in contrast, when using settled dust, in addition to consideration of seasonal influences, it is critical to know the sampling location because the type and level of SVOCs may be related to local materials used there.

Biodegradation of di-(2-ethylhexyl) phthalate by a halotolerant consortium LF.

A halotolerant bacterial consortium capable of degrading di-(2-ethylhexyl) phthalate (DEHP) was enriched from activated sludge. Community analysis revealed that LF contained seven families and seven genera of bacteria. The predominant species was Gordonia sp. (54.93%), Rhodococcus. sp. (9.92%) and Achromobacter sp. (8.47%). The consortium could degrade 93.84% of 1000 mg/l DEHP after 48 h incubation. The optimal temperature and pH for LF to degrade DEHP were 30 °C and 6.0, respectively. LF degraded more than 91% of DEHP with salt concentrations ranging from 0–3%. The inoculum size had great effects on DEHP degradation (incubation time < 24h). LF could degrade high concentrations of DEHP (from 100 to 2000 mg/l) with the degradation ratio above 92% after 72 h incubation. Kinetics analysis revealed that the degradation of DEHP by LF was best fitted by the first-order kinetics when the initial concentration ranged from 100 to 2000 mg/l. The main intermediates (2-ethylhexyl pentyl phthalate, butyl (2-ethylhexyl) phthalate (BEHP), mono-ethylhexyl phthalate (MEHP), mono-hexyl phthalate (MHP), mono-butyl phthalate (MBP)) in DEHP degradation process were identified using gas chromatography–mass spectrometry (GC-MS), and a new complex biochemical pathway was proposed. Furthermore, LF could also degrade dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), di-n-octyl phthalate (DOP) and phthalic acid (PA).

Application of Bioaugmentation Strategy in Biodegradation of Di-n-octyl Phthalate (DOP) in Sequencing Batch Reactor (SBR)

In order to enhance the degradation of Di-n-octyl phthalate (DOP).One bacterial strain was inoculated in SBR. Bioaugmentation by inoculating DOP-degrading bacteria effectively shortened the start-up of SBRs and significantly enhanced DOP degradation in bioreactors (p<0.05), 92.3% DOP removal rate was achieved in consortium bioaugmented SBR, which was double of control SBR. The DOP removal in control reactor was only 37%. The results from this study suggest bioaugmentation is an effective and feasible approach for DOP waste water treatment in practical engineering.

Heterogeneous oxidation of indoor surfaces by gas-phase hydroxyl radicals.

We investigate heterogeneous oxidation kinetics of monolayer-thick, surface-sorbed organics, namely di-n-octyl phthalate (DnOP) and palmitic acid (PA), with gas-phase OH. The pseudo-first order rate constants for organic loss at OH concentrations of 1.6×108 molecules/cm3 are: (2.3±0.1)×10-4 to (4.8±0.8)×10-4 s-1 , and (1.3±0.5)×10-4 s-1 for DnOP and PA, respectively. Films developed in indoor office environments over a few weeks are also oxidized using the same OH concentration. Heterogeneous decay rate constants of mass signals from these films, attributed to phthalates (MW=390.6) and to PA, are similar to those for the single-component films, ie, (1.9±0.4)×10-4 to (3.4±0.5)×10-4 s-1 , and (1.1±0.4)×10-4 s-1 , respectively. These results suggest that the lifetimes for OH heterogeneous oxidation of monolayer-thick indoor organic films will be on the timescale of weeks to months. To support this argument, we present the first analysis of the mass transfer processes that occur when short-lived gas-phase molecules, such as OH, are taken up by reactive indoor surfaces. Due to rapid chemical production, the diffusion limitation to mass transfer is less important for short-lived molecules than for molecules with little chemical production, such as ozone.

Reduced graphene oxide-coated magnetic-nanoparticles as sorbent for the determination of phthalates in environmental samples by micro-dispersive solid-phase extraction followed by ultra-high-performance liquid chromatography tandem mass spectrometry

In this work, the suitability of Fe3O4 nanoparticles coated with reduced-graphene oxide as sorbent was evaluated for the extraction of a group of fourteen phthalic acid esters (i.e. benzylbutyl phthalate (BBP), bis-2-n-butoxyethyl phthalate (DBEP), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), dicyclohexyl phthalate (DCHP), bis-2-ethoxyethyl phthalate (DEEP), diisodecyl phthalate (DIDP), diisononyl phthalate (DINP), bis-isopentyl phthalate (DIPP), bis-(2-methoxyethyl) phthalate (DMEP), dimethyl phthalate (DMP), di-n-octyl phthalate (DNOP), bis-n-pentyl phthalate (DNPP), dipropyl phthalate (DPP)) from environmental samples. Extraction was carried out using magnetic-micro dispersive solid-phase extraction while separation, identification and quantification of the target analytes were achieved by ultra-high-performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry. The methodology was validated for three different types of water samples using dibutyl phthalate-3,4,5,6-d4 as internal standard for all of them. Recovery values ranged from 70 to 120% for the three matrices with relative standard deviation values lower than 20%. Limits of quantification of the method achieved were in the range 6–178 ng/L for all samples and analytes. The methodology was applied for the evaluation of real samples finding the presence of DMP, DPP, BBP, DIBP and DBP in some of the analysed matrices.

Occurrence and fate of phthalate esters in wastewater treatment plants in Qingdao, China

ABSTRACTThe concentrations of 16 phthalate esters (PAEs) were detected in the sewage and sludge from wastewater treatment plants (WWTPs) in Qingdao, China. The total PAE concentrations in the influent samples from the Chengyang, Licun River, and Haibo River WWTPs were 134.42, 186.02, and 135.72 ng/mL, respectively. Dimethyl phthalate (DMP), diethyl phthalate (DEP), dimethylglycol phthalate (DMGP), di(2-ethylhexyl) phthalate (DEHP), di(2-ethoxyethyl) phthalate (DEEP), dicyclohexyl phthalate (DCHP), and di-n-octyl phthalate (DnOP) were all detected, with DMP being the most abundant compound. By contrast, the total PAE concentrations in the effluent samples from the three WWTPs were 39.91, 55.42, and 44.37 ng/mL. The removal efficiencies for individual PAEs in the three WWTPs varied widely. DMP and DEP were removed effectively in the Chengyang WWTP, whereas DMP and DnOP were removed relatively well in the Chengyang and Haibo River WWTPs. In the sludge from the Chengyang, Licun River, and Haibo River WWTPs, the total PAE contents were 96.46 mg/kg, 91.20 mg/kg, and 98.45 mg/kg, respectively. According to the mass balance, most PAEs (48.30%–56.31%) in the sewage decreased, and 43.69%–51.70% of total PAEs were discharged to the environment through the effluent and sludge.

Phthalates removal efficiency in different wastewater treatment technology in the Eastern Cape, South Africa.

The removal capacity of different wastewater treatment plant (WWTP) technologies adopted in rural areas for phthalate was investigated in the Eastern Cape, South Africa. Wastewater samples collected from three selected WWTPs which use activated sludge (AS), trickling filter (TF), and oxidation pond (OP) technology were extracted using the solid-phase extraction method followed by gas chromatography-mass spectrometry (GC-MS) analysis. The six selected phthalate esters (PAEs) dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), di(2-ethyl hexyl) phthalate (DEHP), and di-n-octyl phthalate (DOP) were detected in all the samples collected from the WWTPs. DBP was the most abundant compound in the influent, effluent, and sludge samples with a maximum detection of 2497μgL-1, 24.2μgL-1, and 1249μg/gdW, respectively, followed by DEHP and BBP. There was a relatively high removal capacity achieved by AS in Alice, TF in Berlin, and OP in Bedford with a removal efficiency that varied between 77 and 99%, 76 and 98%, and 61 and 98%, respectively. A high significant correlation of PAE removal with total suspended solids (TSS) and turbidity suggests that the removal performance proceeded more through adsorption on settling particles and sludge than on biodegradation. However, the concentrations of PAEs detected in the final effluent and sludge samples exceeded acceptable levels allowed internationally for a safe aquatic environment. AS may have exhibited a more stable and better performance across the different seasons; however, pollution source control still deserves a special attention to prevent the risk posed by these micropollutants.

Fate and impact of phthalates in activated sludge treated municipal wastewater on the water bodies in the Eastern Cape, South Africa

The concentration and fates of six priority phthalate esters (PAEs); dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP), di (2-ethyl hexyl) phthalate (DEHP), and di-n-octyl phthalate (DOP) in wastewaters from the wastewater treatment plants (WWTPs) which adopted the activated sludge technology in the Amathole Municipality, Eastern Cape, South Africa were investigated. The six PAEs were detected in all the influents and in almost all the WWTP effluent of which DBP was the most abundant in the influent followed by DEHP. Influent concentration of DBP in the three WWTPs ranged between 2.7 and 2488 μgL−1 and the average effluent concentration was 4.90–8.88 μgL−1. On average, the concentration of PAEs in WWTP effluents were higher than PAEs in the upstream and downstream of the discharging point suggesting PAE impact on the receiving water. The concentrations detected in the sludge of which DEHP and DBP were more pervasive ranged between 130 and 1094 μg/g dry weight. The average removal capacity; 27.3–99.5% suggested more adsorption on settling particles and sludge than biodegradation as high significant correlation was found between PAEs removal, total suspended solid and turbidity. Removal of high molecular weight and high octanol-water partition coefficient (logKow) PAEs through adsorption was found to be significantly high. It could be concluded that the release of PAEs into the sludge, and the amount in the final effluent which were found to exceed the acceptable levels allowed internationally, raises safety concern for both aquatic and human's health.