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Structures of dibutyl phthalate (DBP) and di-(2-ethylhexyl) phthalate (DEHP).
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Abstract: Analysis of the natural abundance 14C content of dibutyl phthalate (DBP) from two edible brown algae, Undaria pinnatifida and Laminaria japonica, and a green alga, Ulva sp., revealed that the DBP was naturally produced. The natural abundance 14C content of di-(2-ethylhexyl) phthalate (DEHP) obtained from the same algae was about 50-80% of...
Citations
... DBP varies qualitatively in terms of 14 C content in various sources, petrochemicals, or biologicals. For biological sources, 14 C level exceeds 50%, whereas for petrochemical ones, the level is undetectable (Namikoshi et al. 2006). ...
Epicuticular wax from the leaves of Tillandsia stricta Sol. Sims and Tillandsia usneoides (L.) from Grumari, Marica and Jurubatiba, Rio de Janeiro sandbanks was extracted into chloroform and n-hexane for analyses. The extracts were subjected to gas chromatography (GC-FID) and gas chromatography coupled with mass spectrometry (GC-MS) analyses. In the investigated species, the major n-alkane was found to be C-27. This study has shown that the relation of n-alkanes and fatty acids is a function of the species and the triterpenoids were only observed in the wax of T. usneoides. Phthalates: di-n-octyl phthalate (DNOP), di isobutyl phthalate (DIBP); Di (2-ethylhexyl) phthalate (DEHP), benzoic acid, adipic acid derivatives were also detected beyond of DDT in T. stricta from the Conservation Unit of Jurubatiba. The exposure of T. usneoides to vehicular emission resulted in the reversal of the relationship fatty acid: n-alkanes and the triterpenoids suppression. These results reflect the importance of plants in monitoring environmental purposes and their potential for DDT and phthalates indicator.
... Although some macroalgae, such as Ulva sp., Sargassum sp., Gracialaria sp., or Pterocladia sp., have the remarkable capacity to adsorb lipophilic pollutants [13,30] and endocrine active substances [15], including phthalates [8,48], and can potentially be used for bioremediation approaches, studies have shown that micro-and macroalgae produce phthalates via biosynthetic pathways [33,34,44] probably through the shikimic acid pathway [3,49]. ...
... Using the isotopic labeling approach, it has been observed that di(n-butyl) phthalate and probably di(2-ethylhexyl) phthalate can be biosynthesized by various macroalgae algae such as Undaria pinnatifida, Laminaria japonica, and Ulva sp. [44]. ...
... As previously mentioned, some studies have confirmed that phthalates are produced by algae. These works aim to investigate the origin of phthalates [33,34,44] or consider phthalates as chemical constituents of algae, as observed in chemical characterization of algae [27,38,40] and in studies on the biological activity of algae extracts [18,39,42]. Some studies also suggest that phthalates are naturally present [23] or mention other studies that have reported that they are naturally produced [24]. ...
Phthalic acid esters (PAEs) are a class of ubiquitous and dangerous lipophilic chemicals widely used as additives in various products to improve their physical and chemical properties. Although they have been banned in many countries, their persistence in all environmental compartments is of particular concern. The aquatic environment is especially affected by these compounds because it is strongly influenced both by contamination of anthropic origin and natural contaminants including those produced biosynthetically by some organisms such as algae. In this context, algal organisms can be a source and remedy for phthalate pollution. Both the increase and decrease in uptake and production depend on the physicochemical characteristics of the environment. The dynamics of the natural processes are aimed at achieving an optimal environmental state for their competitiveness and balance of the cellular homeostasis. This review summarizes the studies dealing with biosynthesis and bioaccumulation of phthalates in algae and investigates the source of their origin by suggesting strategies to identify the process leading to their presence.
... VITGV with cytotoxic and antibacterial properties derived from its crude extracts [15,16]. On the other hand, bis (2ethylhexyl) phthalate is an active compound belonging to the family of phthalates which main characters contain aromatic benzene [39]. Interestingly, this corresponding compound was already produced by some Streptomyces spp. with their promising bioactivities including Streptomyces sp. ...
Soil Streptomyces are filamentous Gram-positive bacteria which were the biggest producer of remarkable bioactive compounds with multiple biological roles. This study aimed to assess the antioxidant and cytotoxic activities of crude extract derived from 3 soil Streptomyces strains, namely APM-7, APM-11, and APM-21, which was isolated from Muna Islands, Southeast Sulawesi as well as profiling its compounds using gas chromatography and mass spectrometry (GC-MS). The results indicated that the ethyl acetate extract of APM-7 strain showed the most antioxidant potential with an IC 50 value for both 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2’-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) of 31.61 and 57.91 μ g/mL, respectively. Interestingly, this corresponding extract exhibited the highest total phenolic content (TPC) and total flavonoid content (TFC) values of 41.74 mg GAE/g extract and 32.51 mg QE/g extract. The cytotoxic effect of APM-7 extract (100 μ g/mL) against human breast carcinoma cells (MCF-7) was found as having the best with the inhibition value of 81.31%. GC-MS analysis of APM-7 extract revealed 12 peaks which included some dominant compounds, including isophorone and Bis (2-ethylhexyl) phthalate which might be responsible for the antioxidant and cytotoxic properties. Our results indicate that the Streptomyces sp. strain APM-7 could be developed as medically useful compounds.
... These findings generated a significant discussion regarding the origin of the substance and prompted the debate if it was a true pollutant or a natural metabolite with some biological activities. Therefore, the natural abundance of 14 C content of the relative derivatives of Ulva sp., green algae, and two edible brown algae, Undaria pinnatifida, and Laminaria japonica, were investigated and provided evidence that phthalates can be produced naturally and appropriately (Namikoshi et al., 2006). Furthermore, it was discovered that naturally occurring filamentous fungal strains (Trichoderma asperellum PTN7, Penicillium lanosum PTN121, and Aspergillus niger PTN42) cultivated in either artificial medium or natural water-produced dibutyl phthalate (DBP) through shikimic acid pathway as microbial secondary metabolites (Tian et al., 2016). ...
... Recent studies in the field of isotope analysis indicate the possibility of phthalate biosynthetic pathway in environmental objects (Namikoshi et al. 2006;Chen 2004;Babu and Wu 2010). The evidence of natural origin of phthalates was the content of natural carbon isotope 14 C in di-n-butyl phthalate (DnBP) isolated from the algae Undaria pinnatifida, Laminaria japonica, and Ulva sp. as well as 13 C-labeled DnBP and monoethylhexyl phthalate from freshwater algae and cyanobacteria cell cultured on NaH 13 CO 3 containing media as the sole carbon source. ...
A method for estimating the ratio of stable carbon isotopes ¹³С/¹²С in the composition of phthalates from surface water at a trace concentration level is proposed. It is based on the concentration of hydrophobic components of water using an analytical reversed phase HPLC column followed by their gradient separation and detection of eluted phthalates using a high-resolution time-of-flight mass spectrometer (ESI-HRMS-TOF) in the form of molecular ions. The ratio of stable carbon isotopes ¹³С/¹²C in phthalates is calculated as a ratio of integrals under the monoisotopic [M+1+H]⁺ and [M+H]⁺ peaks. The Δ¹³C value is calculated relatively to the ¹³C/¹²C ratio in commercial DnBP and DEHP phthalates used as standards. The minimal concentration of DnBP and DEHP in water required for a reliable determination of Δ¹³C value is estimated by the level of ca. 0.2 μg L⁻¹. The technique has been verified during the monitoring of priority phthalates in the waters of Lake Baikal.
Graphical abstract
... Since phthalates are not chemically bounded to the polymer matrix, they are able to migrate into the environment during the use and recycling of polymer products. Traces of phthalates can be found in atmospheric aerosol and air, in Recent studies in the eld of isotope analysis indicate the possibility of phthalates biosynthetic pathway in environmental objects (Namikoshi et al. 2006;Chen 2004; Babu and Wu 2010). The evidence of natural origin of phthalates were the content of natural carbon isotope 14 C in di-n-butyl phthalate (DnBP) isolated from the algae Undaria pinnati da, Laminaria japonica, Ulva sp. as well as 13 C-labeled DnBP and monoethylhexyl phthalate from freshwater algae and cyanobacteria cell cultured on NaH 13 CO 3 containing media as the sole carbon source. ...
A method for estimating of the ratio of stable carbon isotopes ¹³ С/ ¹² С in the composition of phthalates from surface water at a trace concentration level is proposed. It is based on the concentration of hydrophobic components of water using an analytical reversed phase HPLC column followed by their gradient separation and detection of eluted phthalates using a high-resolution time-of-flight mass spectrometry (HRMS-TOF) in the form of molecular ions. The ratio of stable carbon isotopes ¹³ С/ ¹² C in phthalates is calculated as a ratio of the peak areas of the monoisotopic masses [M + 1 + H] ⁺ and [M + H] ⁺ . Commercial phthalates, di- n -butyl phthalate (DnBP) and di-(2-ethylhexyl) phthalate (DEHP), were used as standards. The minimal concentration of D n BP and DEHP in water required for a reliable determination of δ ¹³ C value is estimated by the level of ca. 0.2 µg L − 1 . The technique has been verified during the monitoring of priority phthalates in the waters of Lake Baikal.
... Phthalates can be endocrine disrupting chemicals and they exhibit both toxicity and bioaccumulation . Phthalates are also produced by marine algae, with abundance varying among species (Chen, 2004;Namikoshi et al., 2006). Despite the same culture conditions and initial cells density, MC-producing cultures accumulated more cells and higher concentrations of most primary and secondary metabolites than the MC-free cultures at S-phase (Table 1). ...
Cyanobacterial harmful algal blooms (cHABs) dominated by Microcystis aeruginosa threaten the ecological integrity and beneficial uses of lakes globally. In addition to producing hepatotoxic microcystins (MC), M. aeruginosa exudates (MaE) contain various compounds with demonstrated toxicity to aquatic biota. Previously, we found that the ecotoxicity of MaE differed between MC-producing and MC-free strains at exponential (E-phase) and stationary (S-phase) growth phases. However, the components in these exudates and their specific harmful effects were unclear. In this study, we performed untargeted metabolomics based on liquid chromatography-mass spectrometry to reveal the constituents in MaE of a MC-producing and a MC-free strain at both E-phase and S-phase. A total of 409 metabolites were identified and quantified based on their relative abundance. These compounds included lipids, organoheterocyclic compounds, organic acid, benzenoids and organic oxygen compounds. Multivariate analysis revealed that strains and growth phases significantly influenced the metabolite profile. The MC-producing strain had greater total metabolites abundance than the MC-free strain at S-phase, whereas the MC-free strain released higher concentrations of benzenoids, lipids, organic oxygen, organic nitrogen and organoheterocyclic compounds than the MC-producing strain at E-phase. Total metabolites had higher abundance in S-phase than in E- phase in both strains. Analysis of differential metabolites (DMs) and pathways suggest that lipids metabolism and biosynthesis of secondary metabolites were more tightly coupled to growth phases than to strains. Abundance of some toxic lipids and benzenoids DMs were significantly higher in the MC-free strain than the MC-producing one. This study builds on the understanding of MaE chemicals and their biotoxicity, and adds to evidence that non-MC-producing strains of cyanobacteria may also pose a threat to ecosystem health.
... The biogenic origin of DEHP and DBP in Undaria pinnatifida, Laminaria japonica, and green alga Ulva sp. was confirmed by natural 14 C measurements. The natural abundance of 14 C content of DEHP obtained from the same algae was about 50-80% of the standard sample, and the 14 C content of the petrochemical (industrial) products of DBP and DEHP were below the detection limit [52]. Babenko et al. noted that phytoplankton can serve as a source of biogenic PAEs. ...
The increasing consumption of phthalates (PAEs), along with their high toxicity and high mobility, poses a threat to the environment. This study presents initial data on the contents of six priority PAEs in the water of lakes located on the eastern shore of Lake Baikal-Arangatui, Bormashevoe, Dukhovoe, Kotokel, and Shchuchye. The mean total concentrations of the six PAEs in lakes Arangatui and Bormashevoe (low anthropogenic load) were comparable to those in Kotokel (medium anthropogenic load, 17.34 µg/L) but were significantly higher (p < 0.05) than in Dukhovoe and Shchuchye (high anthropogenic load, 10.49 and 2.30 µg/L, respectively). DBP and DEHP were the main PAEs in all samples. The DEHP content in lakes Arangatui and Bormashevoe was quite high, and at some sampling sites it exceeded the MACs established by Russian, U.S. EPA, and WHO regulations. The assessment showed that there is no potential risk to humans associated with the presence of PAEs in drinking water. However, the levels of DEHP, DBP, and DnOP in the water pose a potential threat to sensitive aquatic organisms, as shown by the calculated risk quotients (RQs). It is assumed that the origin of the phthalates in the studied lakes is both anthropogenic and biogenic.
... Dibutyl phtalate (1.58%) was found in SC-CO2 extract of E. amentacea during this study. Its presence can be explained by the fact that brown algae are natural producers of this compound which has the application as plasticizer or solvent in a wide range of industrial products (Namikoshi et al., 2006). Furthermore, the presence of hydrocarbons, such as nonadecane (0.59%) and heptadecane (0.23%), was also detected, as well the presence of terpenes including dihydroactinidiolide (0.13%) and hexahydrofarnesyl acetone (0.20%). ...
Due to the lack of less-volatile compounds composition data of macroalgal supercritical CO2 (SC-CO2) extracts, the main goal of this study was to investigate their chemical profiles. SC-CO2 extraction (40 °C and 300 bar) was performed on seven macroalgal species including five brown (Halopteris filicina, Fucus virsoides, Dictyopteris polypodioides, Gongolaria barbata and Ericaria amentacea), one green (Codium bursa) and one red (Amphiroa rigida), that were collected from the Adriatic Sea. After the analysis by gas chromatography and mass spectrometry, the results revealed that fatty acids were the main components of the extracts. Hexadecanoic acid was found as dominant fatty acid in most of the species, while 3-hexyl-4,5-dithiacycloheptanone was dominant in D. polypodioides. Performed phytochemical study contributes to the knowledge of less-volatile composition of analyzed species indicating that the “species biodiversity“ factor was the most influent regardless of classification to brown, green or red macroalgae.
... The study by Chen (2004) reported that red algae Bangia atropurpurea can de novo synthesize Bis(2-ethylhexyl) phthalate both when cultured in artificial seawater medium and natural seawater medium indicating that the compound was naturally biosynthesized by the red algae. The biosynthetic study conducted by Namikoshi et al. (2006) using isotope 14 C to trace the biosynthesis in seaweeds concluded that dibutyl phthalate isolated from two edible brown and one green seaweeds contained 14 C indicating that the compound was naturally biosynthesized. Di-n-octyl phthalate was found in the seaweeds L. japonica, Ulva sp., Bangia artropurea, Ishige okamurae, Sargassum confusum and S. wighti. ...
A red seaweed Croisettea sp. from Indonesia is reported for the first time. The species was collected from the south coastal area of Yogyakarta, Indonesia. The molecular identification was carried out by amplification of mitochondria gene (cox). The phylogenetic analysis revealed that the red seaweed belongs to the family Kallymeniaceae from the genus Croisettea with 93.3% similarity to Croisettea tasmanica. The ash and protein contents were 16.12% and 14.51% of the dry weight, respectively. Analysis of FT-IR spectra indicated that the seaweed contained galactan sulphate with gelling property. The spectra of GC-MS showed the presence of saturated fatty acids (palmitic acid and stearic acid) and unsaturated fatty acid (oleic acid) and phthalate ester derivative. The spectra of ¹ H-NMR confirmed the presence of the phthalate derivative Bis(2-ethylhexyl phthalate).
