SYSTEMATIC REVIEW


Isolation of Phthalates and Terephthalates from Plant Material – Natural Products or Contaminants?



Thies Thiemann1, *
1 Department of Chemistry, College of Science, United Arab Emirates University, PO Box 15551, Al Ain, United Arab Emirates


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© 2021 Thies Thiemann.

open-access license: This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 International Public License (CC-BY 4.0), a copy of which is available at: https://creativecommons.org/licenses/by/4.0/legalcode. This license permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

* Address correspondence to this author at Department of Chemistry, College of Science, United Arab Emirates University, PO Box 15551, Al Ain, United Arab Emirates; E-mails: thies@uaeu.ac.ae; thiesthiemann@yahoo.de


Abstract

Dialkyl phthalates have been used as plasticizers in polymers for decades. As mobile, small weight molecules, phthalates have entered the environment, where they have become ubiquitous. On the other hand, phthalates continue to be isolated from natural sources, plants, bacteria and fungi as bona fide natural products. Here, doubt remains as to whether the phthalates represent actual natural products or whether they should all be seen as contaminants of anthropogenic origin. The following article will review the material as presented in the literature.

Keywords : Phthalates, Natural product isolation, Contamination, Terephthalates, Pesticides, Agriculture.



1. INTRODUCTION

Phthalates are ubiquitous compounds that have been used as plasticizers in polymers for many decades, starting in the late 1920s – early 1930s, where a number of patents showed the rising interest in these products at the time [1, 2] and where phthalates started to replace camphor-based plasticizers. Phthalates have been especially associated with the emergence of plastics such as polyvinyl chloride [3]. At the same time, phthalates, many of which are environmentally quite mobile, have become pervasive pollutants of our biosphere, entering both water and soil. Although especially the low-MW phthalates can be readily degraded hydrolytically [4], photochemically [5] and microbially [6], detectable amounts of phthalates can be found almost everywhere, including in our diet [7]. Low-MW phthalates are dermally absorbed relatively easily. This leads to the identification of phthalates and phthalate derivatives in humans, easily detectable in urine [8], breast milk [9], and blood [10]. It has been found that the concentrations of phthalates in the air are often higher in urban than in rural areas [11, 12]. Nevertheless, phthalates have been identified in soil, for instance, as leachates from plastic mulching/plastic film greenhouses [13, 14], and also because they are used as agricultural adjuvants in pesticides [15] (Fig. 1).

Phthalates have been isolated from many plants, from algae, bacteria and fungi. In the natural product isolations, oftentimes, the phthalates were looked upon as plant secondary metabolites. As often is the case, after isolation of the products from the plant, the bioactivity of the compounds was studied. In regard to the phthalates, multiple researchers have remarked on various biological activities of the molecules. Intriguing is the comparison of these studies and the investigations of different governmental organizations on the health effects of phthalates as components of consumer products. Sometimes, there can be a disconnect when scientists in closely related but highly specialized, clearly demarcated research areas do not cross-disseminate their fields with information flow. In the case of the study of phthalates, academically, there seem to be rather different areas of research and development that little overlap and often show little data transfer: the development of new product formulations with phthalates, the analytical detection and quantification of phthalates in our daily products and in our environment, often coupled with the assessment of health implications, the study of the degradation of phthalates by bacteria and other microorganisms and lastly the isolation of phthalates as possible natural products from plants and other organisms. In view of the ubiquity of phthalates in our environment, few research papers on the isolation of phthalates from plants have asked whether these products might not be of anthropogenic origin. Nevertheless, two prior review articles have looked at the possibility that at least some of the isolated phthalates could indeed be natural products [16, 17], with a further essay asking the question of whether medicinal plants are polluted with phthalates [18]. In the current contribution, the author reassesses with the aid of published research articles how far phthalates isolated from organisms are indeed natural products or whether they can be seen mostly as contaminants. (Fig. 2)

1.1. Phthalates – Trends in Production and Usage; Health Concerns

Of the roughly 60 different commercially produced phthalates, there are 26 phthalates that are relatively commonly used. The usage of the most common phthalates is shown in Table 1. In 2001, the breakdown of use of different types of phthalates in Europe was reported as follows: di(ethylhexyl) phthalate (DEHP, 9), 51%; diisodecyl phthalate (DIDP), 21%; diisononyl phthalate (DINP, 15), 11%; dibutyl phthalate (5), 2% and others, 17% [19]. At that time, about 8.4 million tons of plasticizer were produced every year. Of DEHP (9), 3.0 million tons were produced in 2006 alone. In the late 2010s, many of the C3-C6 phthalates were replaced with higher MW C9-C13 phthalates [20], with DEHP (9) still abundantly being produced, but in different parts of the world, more and more being replaced by DINP (15). DINP (15) as a “high” phthalate has a longer residency time in plastics, which gives the plastics better durability. It must be noted that while oftentimes the higher branched phthalates are produced as a mixture of isomers, only one isomer for each phthalate is shown in the drawings and tables in the article. Overall, from 2010 onwards, non-phthalate plasticizers are increasingly invading the market. These include terephthalates (Fig. 3), epoxy, trimellitates, and some aliphatics/cycloaliphatics (mainly hydrogenated phtha- lates such as diisononyl cyclohexane-1,2-dicarboxylate [DINCH] which is a mixture of isomers which includes 44), alkane α,ω-dicarboxylates such as di(2-ethylhexyl) adipate (DEHA, 49), and alkane tricarboxylates such as acetyl tri-n-butyl citrate (ATBC, 50) and biomass-derived triglycerides [21]). The market shares of these are forecasted to grow strongly as they continue to replace phthalates [22]. It is estimated that in 2005, 88% of the plasticizers produced were phthalates. The share of admittedly, a growing market declined to 65% in 2017, and it is predicted to decline even further to about 60% in 2022 [22].

Fig. (1). Structures of some of the industrially most important phthalates.

Fig. (2). Phthalates commonly isolated from natural sources.

Table 1. Industrial uses of the most produced phthalates.
Dimethyl phthalate (17) Plasticizer in the production of polyvinyl chloride; coating component in cellulose films; component in laminated safety glasses and shields; as a pesticide (as fermine®); in hair spray (although mostly discontinued in personal care products).
Diethyl phthalate (7) As a fixating agent in fragrances; as excipient and coating material in pharmaceuticals such as in theophylline, erythromycin, verapamil and mianserin formulations.+
Dibutyl phthalate (5) Plasticizer in the production of polyvinyl chloride (PVC), polyvinyl acetate (PVA) and rubber; component in latex adhesives, sealants, car care products, solvent and fixative in cosmetics and paints, insecticides, food wrapping materials, as excipient and coating material in pharmaceuticals such as in mesalazine and lithium.+
Bis(2-ethylhexyl) phthalate (9) Plasticizer in the production of polyvinyl chloride; plasticizer in toys; clothing, incl. shoes; car upholstery; floor tiles; adhesives and paints; plastic tubings for medical instruments.
Bis(2-propylheptyl) phthalate (21) Plasticizer in PVC.
Benzyl butyl phthalate (1) Plasticizer in the production of polyvinyl chloride, polyurethanes, polysulfides and polyacrylates; vinyl flooring, adhesives, car care products, food wrapping material, and artificial leather.
Diisononyl phthalate (15) Plasticizer in the production of polyvinyl chloride; plasticizer in toys; clothing, incl. shoes; adhesives and paints.
Bis(butoxyethyl) phthalate (6) Plasticizer in PVC and PVA; adhesives.
Diisobutyl phthalate (12) Plasticizer in cellulose nitrate.
Diisodecyl phthalate (13) The coating on furnishings, cookware, coating for pharmaceuticals, food wrapping material.
Fig. (3). Terephthalates isolated from natural sources.

This is because of a growing disquiet that phthalates can have harmful effects. DEHP (9) has been found to be an endocrine disruptor [23] and possible carcinogen [24], and DINP (15) has also been put on the list of possible carcinogens [25] by the California Office of Environmental Health Hazard Assessment (OEHHA) in 2013. In fact, butyl benzyl phthalate (BBzP, 1), dibutyl phthalate (DnBP, 5), diethyl phthalate (DEP, 7), diisobutyl phthalate (DiBP, 12), diisononyl phthalate (DINP, 15), di-n-octyl phthalate (DnOP, 20), dipentyl phthalate (DNPP, 9), di-isohexyl phthalate, dicyclohexyl phthalate (DcHP, 11), and di-isoheptyl phthalate have all been associated with illnesses and disorders as diverse as attention-deficit hyperactivity disorder [26], breast cancer [27], obesity [28] and type II diabetes [29], neurodevelopmental issues [30], behavioral issues, autism spectrum disorders [31], altered reproductive development [32] and male fertility issues [33]. It must be said, however, that in many instances, insufficient data is available to make irrefutable statements on the health impacts of phthalates. Some of the compounds replacing phthalates fare a little better. These include the increasingly used terephthalates such as di(2-ethylhexyl) terephthalate. In addition, dimethyl terephthalate (DMT, 18) which is a starting material in the production of terephthalate based plasticizers as well as in the production of polyalkyl terephthalates [34, 35], especially in the synthesis of polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and polybutylene terephthalate (PBT), is looked at as a potential carcinogen and an irritant to skin, eyes and the respiratory tract. As is the case with many monomers and small-molecule starting materials for polymers, also DMT can be found in small concentrations in the respective polymers (Figs. 4 and 5).

1.2. Phthalates in Agricultural Use – Phthalate Content in Soil and Agricultural Produce

There is extensive literature on phthalate content in agricultural produce, whether it be tomatoes grown after biosolids application [36] or radishes grown with sewage sludge and compost application [37]. Extensive developments in analytical chemistry have led to reliable measurement methods for phthalate contents in different types of produce [38] and in processed and packaged foods [39, 40]. The occurrence of phthalates in agricultural soils around the world [41, 42], with many studies originating in China [43-45], has been sufficiently established, where DEHP (9) and DnBP (5) are the most abundant phthalates found. The use of plastic mulching in agriculture is still a widespread technique to suppress weed growth and to contain water needs. While biodegradable polymeric films have been advertised, the by far most often used material is both high and low-density polyethene (LDPE and HDPE). Phthalates are mulch PE additives, where it has been shown that these phthalates are released partially into the soil [46]. The delivery of phthalates from the plastic film covers of the agricultural plants themselves has been studied in some detail [47]. In addition, sewage sludge [42], agrochemicals [48], wastewater irrigation [49] and the atmosphere [50, 51] itself deliver phthalates to the soil [52-54]. Especially, the phthalate uptake of plants from sludge has been a worry [55], where Shea et al. [56] reported a di-n-butyl phthalate (DnBP, 5) uptake in corn at 0.32 ppm from soil contaminated with 100 ppm DnBP (5). The removal of phthalates from agricultural crop derived extracts designated for food or pharmaceutical use is sometimes seen as a necessity and different processes have been developed to that regard [57].

Phthalates can be cleaved to monophthalates and to phthalic acid by UV light [58], but this is a slow process, at least in water with photochemical half-lives of over 100 days (for butyl benzyl phthalate, 1), 3 years (for dimethyl phthalate, 17) and 1000 years [for bis(ethylhexyl)phthalate, 9] [59, 60]. However, as the phthalates penetrate the soil, the degradation pathway open to them is the aerobic or anaerobic ester hydrolysis with subsequent cleavage of the aromatic ring system [61, 62]. Short-chain phthalates such as diethyl phthalate (DEP, 7) are degraded more easily by microorganisms than longer chain phthalates such as bis(2-ethylhexyl) phthalate (DEHP, 9), which can only be co-metabolically degraded in the presence of an additional carbon source [61, 62]. Different microbial strains have been isolated and used to remove phthalates from different matrices, such as natural water (sea water [63]:), soils [64], sediments [65], wastewater [66], and landfills [67]. A recent review of the microbial degradation of phthalates is available [6].

1.3. Phthalates in Aquatic Environments and Isolated from Marine Produce

Monitoring phthalate concentrations in aquatic environments and in marine products has been going on for a long time. A study from Japan, compares the phthalate level of fish caught in the Uji river in 1973 [68] with fish caught there in 1946! A report from 1986 tells us that in the upper Pickwick reservoirs in north Alabama, USA, phthalates have been found to an appreciable degree in turtles, but not in fish or clams [69].

Fig. (4). Isophthalates 46-48, dinonyl cyclohexane-1,2-dicarboxylate isomer (44), and trimellitate 45 as substi-tutes for phthalates as plasticizers.

Fig. (5). Dialkyl alkanedioates and alkenedioates 49, 51, 52, and 56, trialkyl phosphates 55 and cyclosiloxanes 53 and 54, compounds that often accompany phthalates from natural sources.

A study from Portland, Maine, of 1983 tells us the concentration of dibutyl phthalate (5) and di(2-ethylhexyl)phthalate (9) in clams were less than those measured in the sediment [70]. A Chinese study from 2003 looked at the concentration of dibutyl phthalate (5), diethyl phthalate (7) and di(2-ethylhexyl) phthalate (9) in water, soil, sediments, and aquatic organisms, including shrimps, fish and clams from Shanghai, Hangzhou Bay, the Grand Canal and surrounding areas [71]. The presence of phthalates in sponges has been explained to have potentially originated from bacteria on the sponges [72].

Meanwhile, there is also beginning to be a good overview of phthalate concentrations in the aquatic environment in different parts of the world, whether it is in the German Bight [73], the Bay of Marseille [74], or the Asan lake in S.-Korea [75]. In addition, the mobility of phthalates and their movement between the atmosphere and water [73, 76] or between sediments and water become more understood. Investigations were carried out with deuterated di-n-octylphthalate to better comprehend the uptake of phthalates by mollusks from sediments [77].

Phthalates in marine produce are watched carefully. Thus, phthalate concentrations have been assessed and monitored in commercial marine pelagic fish species such as Atlantic bluefin tuna from Sardinia [9-14.62 ng/g DEHP (9); 15.-6.3 ng/g MEHP] [78], Atlantic herring, Atlantic mackerel [17-27 μg/g DIHP (14)] [79], Baltic herring [5.6 μg/g DMP (17)] and codfish [1.9 μg/g DMP (17)] [80]. Phthalate concentrations have also been measured in farmed fish such as in common carp [0.26 mg/kg – 0.72 mg/kg DEHP (9), 0.31 mg/kg - 0.56 mg/kg DnBP, (5)] [81]. How all this translates to exposure of humans to phthalates is an issue of major concern. Already in 1973, D. Williams noted levels of dibutyl phthalate [5, 0-78 ppm] and di(2-ethylhexyl) phthalate [0-160 ppb] in 21 samples of fish available to the Canadian consumer [82]. Since then, a number of studies have looked into the risk of human contact to phthalates through consumption of different types of produce [83-86], be it in Belgian, UK, Tunisian or Chinese markets. Overviews of phthalates in food have been published [87].

1.4. Phthalates Isolated from Organisms as Natural Products – Isolation of Phthalate Replacement Products from Organisms

Against this background, there is a large body of literature concerning the isolation of phthalates from organisms as natural products, i.e., not as or not expressly as contaminants found within the organisms (Table 2). In a number of papers listed here, though, the connection is made between phthalates and plasticizers [88], although it is not precisely noted that the phthalates isolated from the organisms are true of anthropogenic nature. In certain cases, it was not relevant for the authors whether the isolated phthalates were actual plant metabolites or anthropogenic contaminants, such as in the case of identifying the volatile components that make up the bouquet of pineapples of different degrees of ripeness [89], where both dibutyl phthalate (5) and diisobutyl phthalate (12) were found; or in the case of identifying the flavor components of clams and mussels such as from the Hongdao clam [90], where dibutyl phthalate (5) and diethyl phthalate were isolated, or from the muscles of four other Chinese sea clams, where dibutyl phthalate (5) and butyl benzyl phthalate (1) were isolated [91]. In other cases, the authors were very much aware of the possibility of the isolated phthalate being a contaminant. Thus, Silva at al. [92]. were clearly aware that DEHP (9) could be a contaminant from laboratory equipment and state that DEHP (9) was only isolated from Diaporthe phaseolorum and not from other organisms that they worked with under identical conditions. S. E. McKenzie et al. isolated bis (2-ethylhexyl) phthalate from the marine fungus Corollospora lacera, but showed that the compound was indeed an artifact stemming from the culturing and extraction process [93]. Laboratory contamination with phthalates can happen facilely as the author has also experienced in his laboratory, once both in Japan and in the United Arab Emirates. Typical sources of contamination are solvent bottles made of plastic and cling films. Sources, incidents and remedies of such contaminations have been reviewed by Nguyen et al. [94] and Reid et al. [95]. Nevertheless, the overwhelming number of reports on the isolation of phthalates from natural organisms originate from the exposure of these organisms to anthropogenic environmental pollution rather than from contamination of the samples in the laboratory. Oftentimes, phthalates are isolated as a bouquet of different phthalates from the organisms [96-98], often hand-in-hand with alkanedioates such as diisobutyl oxalate (51) and diisobutyl succinate (52) in addition to siloxanes such as hexadecamethylcyclooctasiloxane (53) and octamethylcyclotetrasiloxane (54) that all are known additives in polymers [96]. From the fruits of Acanthopanax sessiliflorus (Araliaceae), 13 different phthalates were isolated [99]. In 2020, N. Kumari et al. published the isolation of dibutyl phthalate (5) as secondary metabolites of an actinomycetes strain grown on actinomycete isolation agar. However, in the same study tert-butylcalix [4] arene, clearly, a synthetic product, was also found as a purported secondary metabolite of the actinomycetes strain [100].

Most of the time, the structures of the phthalates were determined by GC-MS, relying on the retention time of the compounds on the specific column material used and the mass spectrometric data as analyzed by a computer-accessible database. While mostly the data analysis is expected to be correct, such an analysis is not without its danger. Furthermore, isomeric structures, especially of long-chain esters, which in the case of the phthalates are known to be produced industrially oftentimes as isomeric mixtures, are not easily distinguished and need human aided analysis, with multiple mass spectrometric analyses carried out under different conditions. In a number of cases, there is a mismatch between reported and accepted physical data of the phthalates. Thus, DEHP (9) has been isolated from Diaporthe phaseolorum as a dark yellow solid but resembles a colorless oil [92]. Similarly, di-n-butyl phthalate (5), isolated as a secondary metabolite of an endophytic fungal strain of Rumex madaio, has been reported as a solid, although again, the compound is a colorless oil at room temperature [101]. In many cases, however, extensive NMR spectroscopic analyses bear out the structures of the compounds perfectly.

Table 2. Isolation of dialkyl and monoalkyl phthalates from natural sources (organisms).
Phthalate Organism source Description of organism Extracted part of the organism Identification method of the phthalate Region/Location Reference
Benzyl phthalate (24) Hibiscus micranthus Malvaceae root GC/MS Telangana, India K.A. Kumar et al., 2011 [153]
Benzyl butyl phthalate (1) Astilbe chinensis (Saxifragaceae) volatile oil GC/MS China T. Yang et al., 2011 [96]
Bis(7-acetoxy-2-ethyl-5-methylheptyl) phthalate (69) Lonicera quinquelocularis translucent honeysuckle IR, 1H NMR, 13C NMR, DEPT, 1H-COSY, HMBC Pakistan D. Khan et al., 2014 [133]
Bis(2-butoxyethyl)-phthalate (6) Launaea arborecsens Flowering plant
(Asteraceae)
essential oil GC/MS Algerian Sahara A. Cheriti et al., 2006 [154]
Bis (2-methoxycarbonyl-benzoyloxyethyl) ether (74) Cochliobolus lunatus Pathogenic plant fungus 1H NMR China M. Chen et al., 2016 [135]
Bis (2-​ethylbutyl) phthalate (41) Calliandra haematocephala Hassk. Flowering plant (Fabaceae) aerial parts GC/MS Egypt A.H.S. Abou Zeid et al., 2006 [155]
Bis(2-ethyldodecyl) phthalate (34) Hippocampus kuda Bleeler seahorse whole body IR, HRMS, MS, 1H NMR, 13C NMR Zhoushan Island, Zhejiang, China Y. Li et al., 2008 [152]
Bis(2-ethyleicosyl) phthalate (33) Phyllanthus muellerianus Evergreen shrub (Euphorbiaceae) University of Ibadan, Ibadan, Nigeria M. Saleem et al., 2009 [132]
Bis(2-ethyleicosyl) phthalate (33) Nepeta kurramensis Flowering plant (Lamiaceae) 1H NMR, 13C NMR, 2D-NMR, MS Khyber Pakhtunkhwa, Pakistan N. Ur Rehman, 2017 [131]
Bis (2-ethylbutyl) phthalate (41) Holoptelea integrifolia Indian elm leaf, stem, root GC/MS India A. Kavitha et al., 2014 [195]
Di-isopropyl phthalate (42) Streptomyces sp. strain No. A-3315 gram positive bacterium IR, 1H NMR and 13C NMR Kumamoto, Japan M. Uyeda et al., 1990 [148]
Di-isopropyl phthalate (42) Streptomyces bangladeshensis gram positive bacterium
(isolated from soil)
Natore, Bangladesh M.A. Al-Bari et al., 2005 [156]
Bis(2-ethylhexyl) phthalate (9) Calliandra haematocephala Hassk. Flowering plant (Fabaceae) aerial parts GC/MS Egypt A.H.S. Abou Zeid et al., 2006 [155]
Bis(2-ethylhexyl) phthalate (9) Bangia atropurpurea red algae Taiwan C.Y. Chen, 2004 [141]
Bis(2-ethylhexyl) phthalate (9) Aloe vera succulent plant S.-Korea K.H. Lee et al., 2000 [157]
Bis(2-ethylhexyl) phthalate (9) Cryptotaenia canadensis DC. Canadian honewort (perennial plant) Japan S. Hayashi et al., 1967 [158]
Bis(2-ethylhexyl) phthalate (9) Penicillium sp. Endophytic fungus of Curcuma zeodaria IR, 1H NMR and 13C NMR South Sumatra, Indonesia Muharni et al., 2014 [159]
Bis(2-ethylhexyl) phthalate (9) Calotropis gigantea shrub Rajshahi, Bangladesh M. Habib and M.R. Karim, 2009 [143]
M. Habib and M.R. Karim, 2012 [160]
Bis(2-ethylhexyl) phthalate (9) Alchornea cordifolia shrub Leaf, root bark Congo H. Mavar-Manga et al., 2008 [161]
Bis(2-ethylhexyl) phthalate (9) Aspergillus fumigatus Fungus
(isolated from soil samples)
IR, 1H NMR and 13C NMR Mansoura, Egypt M.S. Abdel-Aziz et al., 2017 [162]
Bis(2-ethylhexyl) phthalate (9) Aspergillus awamori fungus 1H NMR, 13C NMR, DEPT-Q NMR Nile river, Egypt M.M. Lotfy et al., 2018 [163]
Bis(2-ethylhexyl) phthalate (9) Brevibacterium McBrellneri gram-positive actinobacterium IR, 1H NMR, 13C NMR India M. Rajamanikyam et al., 2017 [164]
Bis(2-ethylhexyl) phthalate (9) Rheinheimera japonica KMM 9513T marine bacterium Sea of Japan N.I. Kalinovskaya et al., 2017 [165]
Bis(2-ethylhexyl) phthalate (9) Pseudomonas rhizosphaerae marine bacterium China S.H. Qi et al., 2009 [166]
Bis(2-ethylhexyl) phthalate (9) Streptomyces sp. Actinomycete
(isolated from Saharan soil)
1H NMR, 13C NMR, 1H-1H COSY and 1H-13C HMBC NMR Ghardaïa, Algeria E.H. Driche et al., 2015 [167]
Bis(2-ethylhexyl) phthalate (9) Cinachyrella cavernosa (Lamarck) demosponge GC/MS Goa, India S. Wahidullah et al., 2015 [72]
Bis(2-ethylhexyl) phthalate (9) Caulerpa racemosa (O. Dargent) green algae volatile constituents GC/MS Egypt N.E. Awad, 2002 [168]
Bis(2-ethylhexyl) phthalate (9) Codium tomentosum (Stackhouse) green algae volatile constituents GC/MS Egypt N.E. Awad, 2002 [168]
Bis(2-ethylhexyl) phthalate (9) Phyllanthus muellerianus Evergreen shrub (Euphorbiaceae) Pakistan M. Saleem et al., 2009 [132]
Bis(2-ethylhexyl) phthalate (9) Lonicera quinquelocularis translucent honeysuckle 1H NMR, 13C NMR Pakistan D. Khan et al., 2014 [133]
Bis(2-ethylhexyl) phthalate (9) Nocadia levis Actinobacterium
(isolated from laterite soil)
IR, MS, 1H NMR, 13C NMR Guntur, India A. Kavitha et al., 2009 [97]
Bis(2-ethylhexyl) phthalate (9) Cladosporium sp. Marine fungus
(isolated from mangrove stand)
Kei Ling Ha Lo Wai, Sai Kung, Hong Kong, China S.H. Qi et al., 2009 [166]
Bis(2-ethylhexyl) phthalate (9) Stoechospermum marginatum (C. agardh) Kuetzing brown algae whole algae Goa, India S. Wahidulla, 1995 [169]
Bis(2-ethylhexyl) phthalate (9) Ligusticum porteri Apiaceae callus, aerial part, root GC/MS Chihuahua, Mexico, D. Goldhaber-Pasillas et al., 2012 [170]
Bis(2-ethylhexyl) phthalate (9) Ficus carica Tunisian caprifig (Moraceae) Latex of unripe fruit GC/MS Mesjed Aissa agricultural field, Tunisia H. Lazreg-Aref et al., 2012 [171]
Bis(2-ethylhexyl) phthalate (9) Moringa oleifera Drumstick tree
(Moringaceae)
leaf Thanjavur, Tamil Nadu, India S. Karthika et al., 2013 [172]
Bis(2-ethylhexyl) phthalate (9) Streptomyces sp. A-3315 gram positive bacterium cultural filtrate IR, 1H NMR, 13C NMR, Laboratory, Japan M. Uyeda et al., 1990 [148]
Bis(2-ethylheptyl) phthalate (35) Hippocampus kuda Bleeler seahorse Whole body IR, MS, 1H NMR, 13C NMR Zhoushan Island, Zhejiang, China Z.J. Qian et al., 2012 [173]
Y. Li et al., 2008 [152]
Bis(2-ethylheptyl) phthalate (35) Bacillus pumilus Marine gram-positive bacillus MS Bay of Bengal near Andaman and Nicobar islands, India A.M. Priya, 2012 [174]
Bis(5-ethylheptyl) phthalate (35)* Nocadia levis Actinobacterium
(isolated from laterite soil)
IR, MS, 1H NMR, 13C NMR Guntur, India A. Kavitha et al., 2009 [97]
Bis(2-ethylheptyl) 3-nitrophthalate (43) Alstonia boonei Deciduous tropical-forest tree stem bark GC/MS Okpuje, Enugu State, Nigeria A.A. Imam et al., 2017 [175]
Bis(2-ethyldecyl) phthalate (32) Heliotropium strigosum Heliotrope
(Boraginacea)
Whole plant material 1H NMR, 13C NMR, MS Malakand, Pakistan S.M. Shah et al., 2014 [176]
Bis(2-methylheptyl)-phthalate (36) Hypericum hyssopifolium flowering plant UV, IR, 1H NMR, 13C NMR, MS, HRMS Erzurum, Turkey A. Cakir et al., 2003 [102]
Bis(2-methylheptyl)-phthalate (36) Phyllanthus pulcher Tropical leaf-flower (Phyllanthaceae) Malaysia G. Bagalkotkar, 2007 [177]
Bis(2-methylheptyl)-phthalate (36) Bacillus cereus gram-positive bacterium GC/MS India K.M. Anju et al., 2015 [178]
Bis(2-methylheptyl)-phthalate (36) (marine) Pseudomonas sp. PB01 gram negative bacterium 1H NMR, 13C NMR, COSY, DEPT, HMBC NMR GenBank Accession No. EU126129 V.L.T. Hoang et al., 2008 [179]
Bis(2-methylheptyl)-phthalate (36) Chlorophytum boriviliuanum herb root 1H NMR, 13C NMR, DEPT, COSY, HMBC and HMQC Malaysia L.B. Chua et al., 2015 [180]
Bis(2-methylheptyl)-phthalate (36) Vicia villosa Roth hairy vetch (legume) Gyeongsan, S.-Korea M.T. Islam et al., 2013 [181]
Bis(2-methylheptyl)-phthalate (36) Pongamia pinnata Evergreen shrub leaf IR, 1H NMR, 13C NMR Chennai, Tamil Nadu, India P. Rameshthan-gam and P. Ra-masamy, 2007 [182]
Bis(2-methylheptyl)-phthalate (36) Arundina graminifolia (D. Don) Hochr. Bamboo orchid rhizome MS, 1H NMR, 13C NMR China M. Liu et al., 2007 [183]
Bis(2-methylheptyl)-phthalate (36) Lantana camara L. Perennial shrub essential oil GC/MS China L. Ren et al., 2016 [184]
Bis(2-methylheptyl)-phthalate (36) Ponciri fructus (Poncirus trifoliata) Trifoliate orange (Rutaceae) unripen fruit MS S.-Korea A.R. Son et al., 2005 [185]
G.-H. Xu et al., 2008 [186]
Bis(2-methylheptyl)-phthalate (36) Cinnamomi cortex (Cinnamomum cassia Blume) Chinese cinnamom
(tree)
bark MS S.-Korea H.W. Jung et al., 2007 [187]
Bis(2-methylheptyl)-phthalate (36) Phellodendri Cortex Phellodendron amurense Rupr.
Phellodendron chinense Schneid
MS S.-Korea J.G. Lee et al., 2007 [188]
Bis(2-methylheptyl)-phthalate (36) Sarcophyton glaucum Rough leather coral 1H NMR, 13C NMR, 2D-NMR Sanya Bay, Hainan
Island, China
C.X. Zhang et al., 2013 [189]
Bis(2-​propylheptyl) phthalate (21) Flue cured tobacco
(Nicotiana)
Rhizosphere soils of Mengtong of
Shandong province, China
X. Ren et al., 2015 [145]
Bis (2-[2-hydroxymethyl]nonadec-3(E)-enyl)phthalate) (68) Nepeta kurramensis Flowering plant (Lamiaceae) 1H NMR, 13C NMR, 2D-NMR, MS Pakistan N. Ur Rehman et al., 2017 [131]
Bis(3,5,5-trimethylhexyl) phthalate (98) Alstonia boonei Deciduous tropical-forest tree stem bark GC/MS Okpuje, Enugu State, Nigeria A.A. Imam et al., 2017 [175]
2-​Butoxy-​2-​oxoethyl butyl phthalate (99) Trichoderma asperellum filamentous fungus cultural filtrate GC/MS Pantnagar, India N.R. Bhardwaj et al., 2017 [190]
n-Butyl phthalate (25) Desulfovibrio desulfuricans marine bacterium
(from benthal sea water sample)
1H NMR, 13C NMR Dalian sea area, China Y. Zhang et al., 2009 [191]
n-Butyl phthalate (25) Durian fruit (peel) tree volatile constituents of fruit peel GC/MS China B. Zhang et al., 2012 [192]
n-Butyl phthalate (25) Fomitiporia punctata Fungus (Hymenochaetaceae) ethanolic extract GC/MS China F. Zhu et al., 2011 [193]
n-Butyl cyclohexyl phthalate (2) Trichoderma harzianum fungus GC/MS Nani, Allahabad, and Pipri, Faizabad, India A. Mishra et al., 2018 [194]
Butyl decyl phthalate (104) Holoptelea integrifolia Indian elm leaf, root, stem GC/MS India A. Kavitha et al., 2014 [195]
n-Butyl ethyl phthalate (100) Stevia rebaudiana Bert Seasonal plant (Asteraceae) leaf GC/MS Ishurdi, Pabna, Bangladesh M.A. Hossain et al., 2010 [196]
n-Butyl n-hexyl phthalate (101) Curvularia senegalensis Filamentous fungus
(isolated from soil)
culture medium GC/MS Brazil E.M.F. Lucas et al., 2008 [108]
n-Butyl-isobutyl phthalate (95) Lentzea violacea AS 08 Actinobacterium
(isolated from soil of Himalayan ecosystem)
IR, MS, 1H NMR, 13C NMR, HSQC NMR Himalaya, India A. Hussain et al., 2017 [197]
n-Butyl-isobutyl phthalate (95) Laminaria japonica kelp 1H NMR, 13C NMR, MS Rongcheng, China T. Bu et al., 2010 [149]
n-Butyl-isobutyl phthalate (95) Melodinus fusiformis Plant (Apocynaceae) leaf, twig GC/MS China D. Wang et al, 2012 [198]
n-Butyl-isobutyl phthalate (95) Dalbergia cochinchinensis Thailand rosewood (Fabaceae) 1H NMR, 13C NMR Fangchenggang, Guangxi, China R. Liu et al., 2015 [199]
n-Butyl-isobutyl phthalate (95) Lythrum salicaria Flowering plant whole plant GC/MS Sapporo, Japan E. Fujita et al., 1972 [200]
n-Butyl-isobutyl phthalate (95) Trichoderma harzianum fungus GC/MS Nani, Allahabad, and Pipri, Faizabad, India A. Mishra et al., 2018 [194]
n-Butyl-2-(8-methylnonyl) phthalate (106) Trichoderma asperellum filamentous fungus culture filtrate GC/MS Pantnagar, India N.R. Bhardwaj et al., 2017 [190]
n-Butyl nonyl phthalate
(103)
Trichoderma harzianum fungus GC/MS Nani, Allahabad, and Pipri, Faizabad, India A. Mishra et al., 2018 [194]
n-Butyl octyl phthalate (102) Alnus nitida West Himalayan alder stem bark GC/MS Swat, Pakistan M. Sajid et al., 2017 [201]
n-Butyl octyl phthalate (102) Trichoderma asperellum filamentous fungus culture filtrate GC/MS Pantnagar, India N.R. Bhardwaj et al., 2017 [190]
n-Butyl octyl phthalate
(102)
Canthium parviflorum Lam. (Plectoria parviflora) (Rubiaceae) callus, leaf GC/MS Andhra Pradesh, India S.C. Kala et al., 2017 [202]
n-Butyl octyl phthalate
(102)
Amaranthus caudatus L. annual flowering plant GC/MS China L.Y. Qin et al., 2015 [98]
n-Butyl octyl phthalate
(102)
Launaea arboresens Flowering plant
(Asteraceae)
essential oil GC/MS Algerian Sahara A. Cheriti et al., 2006 [154]
n-Butyl undecyl phthalate
(105)
Brassica juncea L. mustard plant leaf GC/MS Punjab, India A. Sharma et al., 2017 [203]
n-Butyl undecyl phthalate
(105)
Cenchrus ciliaris Dhaman grass whole plant GC/MS Jodhpur, Rajasthan, India P. Singariya et al., 2015 [204]
Didecyl phthalate (108) Caulerpa racemosa (O. Dargent) green algae volatile constituents GC/MS Egypt N.E. Awad, 2002 [168]
Didecyl phthalate (108) Codium tomentosum (Stackhouse) green algae volatile constituents GC/MS Egypt N.E. Awad, 2002 [168]
Didodecyl phthalate (110) Brassica juncea L. mustard plant leaf GC/MS Punjab, India A. Sharma et al., 2017 [203]
Diethyl phthalate (7) Helicobacter pylori gram negative bacterium culture filtrate GC/MS, HPLC Californian laboratory, USA Keire et al., 2001 [205]
Diethyl phthalate (7) Canthium parviflorum Lam. (Plectoria parviflora) (Rubiaceae) callus, leaf GC/MS Andhra Pradesh, India S.C. Kala et al., 2017 [202]
Diethyl phthalate (7) Moringa oleifera Drumstick tree
(Moringaceae)
root GC/MS HEJICCBS garden, University of Karachi, Pakistan S. Faizi et al., 2014 [206]
Diethyl phthalate (7) Moringa oleifera Drumstick tree
(Moringaceae)
leaf Thanjavur, Tamil Nadu, India S. Karthika et al., 2013 [172]
Diethyl phthalate (7) Tecoma radicans (Campsis radicans) Bignoniaceae leaf GC/MS Egypt F.A. Hashem et al., 2006 [207]
Diethyl phthalate (7) Artocarpus lakoocha Roxb. leaf GC/MS Kolkata, India E. Bhattacharya, et al., 2019 [208]
Diethyl phthalate (7) Penicillium olsonii filamentous fungus Cultural filtrate IR, EI-MS, 1H NMR, 13C NMR Laboratory, France P. Amade et al., 1994 [209]
Dimethyl phthalate (7) Amaranthus caudatus L. annual flowering plant GC/MS China L.Y. Qin et al., 2015 [98]
Dimethyl phthalate (7) Eucryphia cordifolia Cav. Chilean Ulmo
(Cunoniaceae)
honey GC/MS Puerto Varas, Chile E. Acevedo et al., 2017 [210]
Dimethyl phthalate (7) Syzygium cumini Malabar plum (Myrtaceae) bark GC/MS Madhya Pradesh, India Mehta, B.K. et al., 2012 [211]
Dimethyl phthalate (7) Cryptotaenia canadensis DC. Canadian honewort (perennial plant) Japan S. Hayashi et al., 1967* [158]
Di-n-amyl phthalate (19) Cryptotaenia canadensis DC. Japan S. Hayashi et al., 1967* [158]
Di-n-butyl phthalate (5) Cryptotaenia canadensis DC. Japan S. Hayashi et al., 1967* [158]
Di-n-butyl phthalate (5) Calliandra haematocephala Hassk. Flowering plant (Fabaceae) aerial parts GC/MS Egypt A.H.S. Abou Zeid et al., 2006 [155]
Di-n-butyl phthalate (5) Cladophora fracta green algae GC/MS Different locations in Taiwan B. Babu and J.-T. Wu, 2010 [212]
Di-n-butyl phthalate (5) Sargassum confusum brown macroalgae whole algae 1H NMR, 13C NMR, MS S.-Korea V.S. Ganti et al., 2006 [213]
Di-n-butyl phthalate (5) Streptomyces nasri gram positive bacterium 1H NMR, 13C NMR Laboratory, Egypt M.Y.M. El-Naggar, 1997 [214]
Di-n-butyl phthalate (5) Chlorella sp. single-celled green algae GC/MS Different locations in Taiwan B. Babu and J.-T. Wu, 2010 [212]
Di-n-butyl phthalate (5) Launaea arboresens Flowering plant
(Asteraceae)
essential oil GC/MS Algerian Sahara A. Cheriti et al., 2006 [154]
Di-n-butyl phthalate (5) Cinachyrella cavernosa (Lamarck) demosponge GC/MS Goa, India S. Wahidullah et al., 2015 [72]
Di-n-butyl phthalate (5) Bangia atropurpurea red algae Taiwan C.Y. Chen, 2004
[141]
Di-n-butyl phthalate (5) Hydrodictyon reticulatum water net
green algae
GC/MS Different locations in Taiwan B. Babu and J.-T. Wu, 2010 [212]
Di-n-butyl phthalate (5) Microcystis aeruginosa freshwater cyanobacterium GC/MS Different locations in Taiwan B. Babu and J.-T. Wu, 2010 [212]
DI-n-butyl phthalate (5) Phormidium sp. cyanobacterium GC/MS Different locations in Taiwan B. Babu and J.-T. Wu, 2010 [212]
Di-n-butyl phthalate (5) Undaria pinnatifida edible seaweed
(wakame, sea mustard)
14C natural abundance measurements Kanazawahakkei, Yokohama, Japan M. Namikoshi et al., 2006 [215]
Di-n-butyl phthalate (5) Laminaria japonica brown algae 14C natural abundance measurements Hachinohe, Aomori, Japan M. Namikoshi et al., 2006 [215]
Di-n-butyl phthalate (5) Stoechospermum marginatum (C. agardh) Kuetzing brown algae whole algae Goa, India S. Wahidulla, 1995 [169]
Di-n-butyl phthalate (5) Ulva sp. edible green algae
sea lettuce
14C natural abundance measurements Yokohama Marine Park, Yokohama, Japan M. Namikoshi et al., 2006 [215]
Di-n-butyl phthalate (5) Spirogyra sp. filamentous green algae (water silk) GC/MS Various locations in Taiwan B. Babu and J.-T. Wu, 2010 [212]
Di-n-butyl phthalate (5) Caulerpa racemosa (O. Dargent) green algae volatile constituents GC/MS Egypt N.E. Awad, 2002 [168]
Di-n-butyl phthalate (5) Streptomyces melanosporofaciens gram-positive bacterium S.-Korea D.-S. Lee, 2000 [216]
Di-n-butyl phthalate (5) Streptomyces albidoflavus gram-positive bacterium Laboratory, India R. N. Roy et al., 2006 [217]
Di-n-butyl phthalate (5) Trichoderma harzianum fungus GC/MS Nani, Allahabad, and Pipri, Faizabad, India A. Mishra et al., 2018 [194]
Di-n-butyl phthalate (5) Rhizosphere actinomycetes gram-positive, filamentous bacterium Isolated from soil samples GC/MS Kota, Jaipur, Alwar, Udaipur in Rajasthan, India N. Kumari et al., 2020 [100]
Di-n-butyl phthalate (5) Endophytic fungus of Rumex madaio Endophytic fungus 1H NMR, 13C NMR Putuo Island, Zhoushan, China X. Bai et al., 2019 [101]
Di-n-butyl phthalate (5) Flowers of Sophora japonica var. violacea Japanese pagoda tree 1H NMR, 13C NMR Dalian, China J. Yang et al., 2018 [218]
Di-n-butyl phthalate (5) Salicornia herbacea halophyte flowering plant 1H NMR, MS Yancheng City, Jiangsu, China X. M. Wang et al., 2013 [219]
Di-n-butyl phthalate (5) Melodinus fusiformis Plant (Apocynaceae) leaf, twig GC/MS China D. Wang et al., 2012 [198]
Di-n-butyl phthalate (5) Nocardia levis MK-Vl_113 actinobacterium MS of a mixture Guntur, India A. Kavitha et al., 2010 [220]
A. Kavitha et al., 2009 [97]
Di-n-butyl phthalate (5) Streptomyces sp. strain 6803 gram-positive bacterium China M. Chen et al., 2009 [221]
Di-n-butyl phthalate (5) Trichoderma asperellum filamentous fungus China C. Tian et al., 2016 [142]
Di-n-butyl phthalate (5) Aspergillus niger filamentous fungus China C. Tian et al., 2016 [142]
Di-n-butyl phthalate (5) Ipomoea carnea flowering plant (pink morning glory) 1H NMR and 13C NMR Puna, India E. Khatiwora et al., 2011 [222]
V.B. Adsul et al., 2012 [223]
Di-n-butyl phthalate (5) Callianthemum taipaicum rhizomatous herb MS, 1H NMR, 13C NMR Taibai Mt., Shaanxi, China D.M. Wang et al., 2012 [224]
Di-n-butyl-phthalate (5) Zygomycale sp. marine sponge GC-MS J.A. Johnson et al., 2012 [225]
Di-n-butyl phthalate (5) (marine) Pseudomonas sp. PB01 gram negative bacterium 1H NMR, 13C NMR, COSY, DEPT, HMBC NMR GenBank Accession No. EU126129 V.L.T. Hoang et al., 2008 [179]
Di-n-butyl phthalate (5) Paraconiothyrium variabile (fungus) on Aquilaria sinensis (plant) fungus producing agilawood GC/MS China J.L. Cui et al., 2013 [226]
Di-n-butyl phthalate (5) Sisymbrium officinale hedge mustard (plant) Split, Croatia I. Blažević et al., 2010 [227]
Di-n-butyl phthalate (5) Brevibacterium McBrellneri gram positive actinobacterium IR, 1H NMR, 13C NMR MTCC, IMTECH, Chandigarh, India (procurement) M. Rajamanik-yam et al., 2017 [164]
Di-n-butyl phthalate (5) Rheinheimera japonica KMM 9513T marine bacterium Sea of Japan N.I. Kalinovskaya et al., 2017 [165]
Di-n-butyl phthalate (5) Exserohilum monoceras fungus GC/MS China Y. Chen et al., 2009 [228]
Di-n-butyl phthalate (5) Pseudomonas stutzeri gram negative bacterium China X.J. Gu et al., 2011 [229]
Di-n-butyl phthalate (5) Aspergillus parasiticus grown on hazelnuts fungus HPLC-MS P. Basaran et al., 2010 (authors qualify that the phthalate can be of anthropo-genic origin) [230]
Di-n-butyl phthalate (5) Uncaria rhynchophylla Plant (Cat’s claw herb) NMR, MS China (market purchased material) Y.-L. Wang et al., 2018 [231]
Di-n-butyl phthalate (5) Leucas zeylanica Ceylon slitwort
(Lamiaceae)
NMR, incl. 2D-NMR, MS Haikou, China N. Nidhal et al., 2020 [232]
Di-n-butyl phthalate (5) Dolomiaea souliei Flowering plant (Asteraceae) China H. Wei et al., 2012 [233]
Di-n-butyl phthalate (5) Durian fruit (peel) tree volatile constituents of fruit peel GC/MS China B. Zhang et al., 2012 [192]
Di-n-butyl phthalate (5) Lantana camara L. Perennial shrub essential oil GC/MS China L. Ren et al., 2016 [184]
Di-n-butyl phthalate (5) Sarcophyton glaucum Rough leather coral 1H NMR, 13C NMR, 2D-NMR Sanya Bay, Hainan
Island, China
C.X. Zhang et al., 2013 [189]
Di-n-butyl phthalate (5) Lythrum salicaria Flowering plant whole plant GC/MS Sapporo, Japan E. Fujita et al., 1972 [200]
Di-n-butyl phthalate (5) Verbena venosa, V. hybrida, V. supina, V. bonariensis Flowering plant volatile components of aerial parts GC/MS Nasar City, Cairo, Egypt H. Al-Amier et al., 2005 [234]
Di-n-butyl phthalate (5) Trichoderma asperellum filamentous fungus culture filtrate GC/MS Pantnagar, India N.R. Bhardwaj et al., 2017 [190]
Di-n-butyl phthalate (5) Coleus foskohlii
(Plectranthus barbatus)
Perennial plant essential oil GC/MS India S. Takshak et al., 2016 [235]
Di-n-butyl phthalate (5) Rhizophora apiculata Mangrove plant leaf GC/MS Tamil Nadu, India C.C.J. Paranjothi et al., 2018 [236]
Di-n-butyl phthalate (5) Lysimachia microcarpa (Primulaceae) essential oil GC/MS China Z. Ding et al., 1993 [237]
Di-n-butyl phthalate (5) Capsicum chinense Chili pepper
(Solanaceae)
Root exudate GC/MS China X. Han, et al., 2015 [238]
Di-n-butyl phthalate (5) Cupressus sempervirens Mediterranean cypress (Cupressaceae) bark and leaf GC/MS Al-Jabel Al-Akhdar Region, Libya M.E.I. Badawy et al., 2019 [239]
Di-n-butyl phthalate (5) Tecoma radicans (Campsis radicans) Bignoniaceae leaf GC/MS Egypt F.A. Hashem et al., 2006 [207]
Di-n-butyl phthalate (5) Morus alba White mulberry leaf GC/MS Aceh, Indonesia R. Nasution et al., 2015 [240]
Di-n-butyl phthalate (5) Morus alba White mulberry leaf GC/MS China Y. Yang et al., 2011 [241]
Di-n-butyl phthalate (5) Brosimum glaziovii Moraceae Leaf and branch GC/MS Botanical Garden, Sao Paulo, Brazil A. Coqueiro et al., 2014 [242]
Di-n-butyl phthalate (5) Artocarpus nanchuanensis Moraceae Fruiting branch 1H and 13C NMR Nanchuan
District, Chongqing City, China
G. Ren et al., 2013 [243]
Di-n-butyl phthalate (5) Ficus benghalensis L. Moraceae Stem bark GC/MS Egypt F. Darwish, 2002 [244]
Dicyclohexyl phthalate (11) Sargassum confusum brown macroalgae whole algae 1H NMR, 13C NMR S.-Korea V.S. Ganti et al., 2006 [213]
Dicyclohexyl phthalate (11) Tecoma radicans (Campsis radicans) Bignoniaceae leaf GC/MS Egypt F.A. Hashem et al., 2006 [207]
Diethyl phthalate (7) Avicennia officinalis Indian mangrove GC/MS Tamil Nadu, India V.B. Bhimba et al., 2013 [245]
Diethyl phthalate (7) Streptomyces cheonanensis VUK-A gram-positive bacterium
(isolated from mangrove ecosystem)
Coringa, Gulf of Bengal, Andhra Pradesh U. Mangamuri et al., 2016 [246]
Diethyl phthalate (7) Vicia villosa Roth Hairy vetch (legume) Gyeongsan, S.-Korea M.T. Islam et al., 2013 [181]
Diethyl phthalate (7) Syzygium cumini Malabar plum (Myrtaceae) bark GC/MS Madhya Pradesh, India Mehta, B.K. et al., 2012 [211]
Diethyl phthalate (7) Undaria pinnatifida edible seaweed
(wakame, sea mustard)
14C natural abundance measurements Kanazawahakkei, Yokohama, Japan M. Namikoshi et al., 2006 [215]
Diethyl phthalate (7) Laminaria japonica brown algae 14C natural abundance measurements Hachinohe, Aomori, Japan M. Namikoshi et al., 2006 [215]
Diethyl phthalate (7) Ulva sp. edible green algae
sea lettuce
14C natural abundance measurements Yokohama Marine Park, Yokohama, Japan M. Namikoshi et al., 2006 [215]
2, 12-Diethyl-11-methylhexadecyl 2-ethyl-11-methylhexadecyl phthalate (96) Hippocampus kuda Bleeler seahorse Whole body HRMS, MS, IR, UV, 1H NMR, 13C NMR Zhoushan Island, Zhejiang, China Z.J. Qian et al., 2012 [173]
Y. Li et al., 2008 [152]
Di-n-heptyl phthalate (111) Trichoderma asperellum filamentous fungus culture filtrate GC/MS Pantnagar, India N.R. Bhardwaj et al., 2017 [190]
Di-n-hexyl phthalate (14) Cryptotaenia canadensis DC. Canadian honewort (perennial plant) Japan S. Hayashi et al., 1967* [158]
Di-n-hexyl phthalate (14) Ligusticum porteri Apiaceae callus, aerial part, root GC/MS Chihuahua, Mexico, D. Goldhaber-Pasillas et al., 2012 [170]
Di-n-hexyl phthalate (14) Verbena venosa, V. hybrida, V. supina, V. bonariensis Flowering plant volatile components of aerial parts GC/MS Nasar City, Cairo, Egypt H. Al-Amier et al., 2005 [234]
Di-n-hexyl phthalate (14) Flue cured tobacco
(Nicotiana)
Rhizosphere soils of Mengtong of
Shandong province, China
X. Ren et al., 2015 [145]
Di-n-hexyl phthalate (14) Trichoderma asperellum filamentous fungus culture filtrate GC/MS Pantnagar, India N.R. Bhardwaj et al., 2017 [190]
Di-n-hexyl phthalate (14) Ficus carica L Common fig volatile oil GC/MS China J. Tian et al., 2005 [247]
Diisobutyl phthalate (12) Telfairia occidentalis Hook Fluted pumpkin (Cucurbitaceae) seed GC/MS Uyo, Nigeria O.A. Eseyin et al., 2018 [248]
Diisobutyl phthalate (12) Amaranthus caudatus L. annual flowering plant GC/MS China L.Y. Qin et al., 2015 [98]
Isobutyl 2-pentyl phthalate (112) Trichoderma harzianum fungus GC/MS Nani, Allahabad, and Pipri, Faizabad, India A. Mishra et al., 2018 [194]
Di-isooctyl phthalate (16)*** Sclerotium cepivorum Fungus (Ascomycota) GC/MS Dakahlia and Gharbia,
Egypt
E.A. Elsherbiny et al., 2015 [249]
Di-isooctyl phthalate (16) Telfairia occidentalis Hook Fluted pumpkin (Cucurbitaceae) seed GC/MS Uyo, Nigeria O.A. Eseyin et al., 2018 [248]
Di-isooctyl phthalatex Amaranthus caudatus L. annual flowering plant GC/MS China L.Y. Qin et al., 2015 [98]
Di-isooctyl phthalate (16) Ficus carica L Common fig volatile oil GC/MS China J. Tian et al., 2005 [247]
Di-isononyl phthalate (DINP-2)**** (15) Pterocarpus erinaceus tree stem bark GC/MS Nsukka, Enugu State, Nigeria A.F. Gabriel et al., 2009 [250]
Di-isononyl phthalate (15) Sclerotium cepivorum Fungus (Ascomycota) GC/MS Dakahlia and Gharbia,
Egypt
E.A. Elsherbiny et al., 2015 [249]
Di-isononyl phthalate (15) Calliandra haematocephala Hassk. Flowering plant (Fabaceae) aerial parts GC/MS Egypt A.H.S. Abou Zeid et al., 2006 [155]
Di-isononyl phthalate (15) Caulerpa racemosa (O. Dargent) green algae volatile constituents GC/MS Egypt N.E. Awad, 2002 [168]
Di-isononyl phthalate (15) Codium tomentosum (Stackhouse) green algae volatile constituents GC/MS Egypt N.E. Awad, 2002 [168]
Di-isononyl phthalate (15) Sargassum confusum brown macroalgae whole algae 1H NMR, 13C NMR S.-Korea V.S. Ganti et al., 2006 [213]
Di-isononyl phthalate (15) Astragalus membranaceus Flowering plant (Fabaceae) root S.-Korea J.S. Kim et al., 1996 [251]
Di-isononyl phthalate (15) Stoechospermum marginatum (C. agardh) Kuetzing brown algae whole algae Goa, India S. Wahidulla, 1995 [169]
Di-n-pentyl phthalate (19) Trichoderma asperellum filamentous fungus culture filtrate GC/MS Pantnagar, India N.R. Bhardwaj et al., 2017 [190]
Di-n-pentyl phthalate (19) Sindora glabra tree (Fabaceae) leaf China J.F. Zhang et al., 2016 [252]
Di-n-pentyl phthalate (19) Chaenomeles sinensis
(Pseudocydonia sinensis)
Chinese quince
(deciduous tree)
fruit China H.Y. Liang et al., 2013 [253]
Di-n-pentyl phthalate (19)******* Codonopsis pilosula perennial flowering plant 1H NMR, 13C NMR, MS Tanchang country, Gansu Province, China N. Xie et al., 2017 [254]
Ditridecyl phthalate (40) Rhododendron arboreum Sm tree rhododendron
(Ericaceae)
flower GC/MS Punjab, India V. Gautam et al., 2016 [255]
Ditridecyl phthalate (40) Ficus carica L Common fig volatile oil GC/MS China J. Tian et al., 2005 [247]
Ethyl phthalate (62) Patrinia villosa Juss (Caprifoliaceae) essential oil GC/MS China X.P. Liu et al., 2008 [256]
Ethyl methyl phthalate (23) Carduus pycnocephalus L. Italian thistle essential oil GC/MS Al-Hada, Saudi Arabia L.A. Al-Shammari et al., 2012 [111]
Ethyl methyl phthalate (23) Datura stramonium L. Thorn apple stem GC/MS, FT-IR Turkey H. Durak and T. Aysu, 2016 [110]
Ethyl methyl phthalate (23) Isatis indigotica Dyer’s woad liposoluble constituents GC/MS China J. Wu et al., 2008 [112]
Ethyl methyl phthalate (23) Salvia sclarea L. Clary sage volatile oils GC/MS, GC/FTIR China J. Cai et al., 2006 [257]
n-Heptyl n-propyl phthalate (114) Curvularia senegalensis Filamentous fungus
(isolated from soil)
culture medium GC/MS Brazil E.M.F. Lucas et al., 2008 [108]
n-Hexyl phthalate (27) Hirsutella citriformis fungus GC/MS India A. Ramachan-dran et al., 2013 [258]
n-Hexyl n-propyl phthalate (113) Curvularia senegalensis Filamentous fungus
(isolated from soil)
culture medium GC/MS Brazil E.M.F. Lucas et al., 2008 [108]
2-(4-Hydroxybutyl)butyl methyl phthalate (116) Alnus nitida West Himalayan alder stem bark GC/MS Swat, Pakistan M. Sajid et al., 2017 [201]
Cyclohexyl phthalate (117) Polygonum aviculare Common knotgrass Essential oil GC/MS China F.Q. Xu et al., 2012 [259]
Decyl butyl phthalate (2 undefined isomers) (104) Curvularia senegalensis Filamentous fungus
(isolated from soil)
culture medium GC/MS Brazil E.M.F. Lucas et al., 2008 [108]
Decyl butyl phthalate (104) Telfairia occidentalis Fluted pumpkin (Cucurbitaceae) seed GC/MS Uyo, Nigeria O.A. Eseyin et al., 2018 [248]
Di-isoamyl phthalate (118) Cryptotaenia canadensis DC. Canadian honewort (perennial plant) Japan S. Hayashi et al., 1967* [158]
Di-isobutyl phthalate (12) Cryptotaenia canadensis DC. Canadian honewort (perennial plant) Japan S. Hayashi et al., 1967* [158]
Di-isobutyl phthalate (12) Streptomyces sp. strain 6803 gram-positive bacterium China M. Chen et al., 2009 [221]
Di-isobutyl phthalate (12) Rheinheimera japonica KMM 9513T marine bacterium Sea of Japan N.I. Kalinovskaya et al., 2017 [165]
Di-isobutyl phthalate (12) Aquilariae resinatum (Thymelaeaceae) volatile components GC/MS Hainan, China N. Lin et al., 2016 [260]
Di-isobutyl phthalate (12) Scaligeria nodosa flowering plant (Apiaceae) essential oil GC/MS Bamu Mt., Shiraz, Iran A.R. Jassbi et al., 2017 [261]
Di-isobutyl phthalate (12) Lantana camara L. Perennial shrub essential oil GC/MS China L. Ren et al., 2016 [184]
Di-isobutyl phthalate (12) Lythrum salicaria Flowering plant whole plant GC/MS Sapporo, Japan E. Fujita et al., 1972 [200]
Di-isobutyl phthalate (12) Trichoderma asperellum filamentous fungus culture filtrate GC/MS Pantnagar, India N.R. Bhardwaj et al., 2017 [190]
Di-isobutyl phthalate (12) Rhizophora apiculata Mangrove plant leaf GC/MS Tamil Nadu,
India
C.C.J. Paranjothi et al., 2018 [236]
Di-isobutyl phthalate (12) Holoptelea integrifolia Indian elm root, stem, leaf GC/MS India A. Kavitha et al., 2014 [195]
Di-isobutyl phthalate (12) Astilbe chinensis (Saxifragaceae) volatile oil GC/MS China T. Yang et al., 2011 [96]
Di-isobutyl phthalate (12) Capsicum chinense Chili pepper
(Solanaceae)
Root exudate GC/MS China X. Han et al., 2015 [238]
Di-isopropyl phthalate (42) Cinachyrella cavernosa demosponge GC/MS Goa, India S. Wahidullah et al., 2015 [72]
Di-n-octyl phthalate (20) Sargassum confusum brown macroalgae whole algae 1H NMR, 13C NMR, MS S.-Korea V.S. Ganti et al., 2006 [213]
Di-n-octyl phthalate (20) Sargassum wightii brown macroalgae India V.M.V.S. Sastry et al., 1995 [262]
Di-n-octyl phthalate (20) Salicornia herbacea halophyte flowering plant 1H NMR, MS Yancheng City, Jiangsu, China X. M. Wang et al., 2013 [219]
Di-n-octyl phthalate (20) Launaea arboresens Flowering plant
(Asteraceae)
essential oil GC/MS Algerian Sahara A. Cheriti et al., 2006 [154]
Di-n-octyl phthalate (20) Streptomyces parvus gram-positive bacterium
(from seawater and sediment samples)
GC/MS Suez Bay, Egypt H. Abd-Elnaby et al., 2016 [263]
Di-n-octyl phthalate (20) Nigella glandulifera Freyn. annual plant
(Ranunculaceae)
D.T.M. Nguyen et al., 2007 [151]
Di-n-octyl phthalate (20) Lonicera quinquelocularis translucent honeysuckle 1H NMR, 13C NMR Pakistan D. Khan et al., 2014 [133.134]
Di-n-octyl phthalate (20) Lythrum salicaria Flowering plant whole plant GC/MS Sapporo, Japan E. Fujita et al., 1972 [200]
Di-n-octyl phthalate (20) Trichoderma asperellum filamentous fungus culture filtrate GC/MS Pantnagar, India N.R. Bhardwaj et al., 2017 [190]
Diisooctyl phthalate (16) Fomitiporia punctata Fungus (Hymenochaetaceae) ethanolic extract GC/MS China F. Zhu et al., 2011 [193]
Diisooctyl phthalate (16) Trichoderma harzianum fungus GC/MS Nani, Allahabad, and Pipri, Faizabad, India A. Mishra et al., 2018 [194]
Di-n-octyl phthalate (20) Hibiscus micranthus Malvaceae root GC/Ms Telangana, India K.A. Kumar et al., 2011 [153]
Di-n-octyl phthalate (20) Cenchrus ciliaris Dhaman grass whole plant GC/MS Jodhpur, Rajasthan, India P. Singariya et al., 2015 [204]
Di-n-octyl phthalate (20)***** Euphorbia thymifolia annual plant whole plant GC/MS Madhya Pradesh, India R. Shrivastava et al., 2019 [264]
Di-n-octyl phthalate (20) Pachygone ovata climbing shrub India L.E. Amalarasi et al., 2019 [150]
Di-n-octyl phthalate (20) Saccharomyces cerevisiae baker’s yeast GC/MS M.M. Abdel-Kareem et al., 2019 [265]
Di-n-octyl phthalate (20) Plumbago zeylanica, Linn. herbaceous plant leaf GC/MS Jaipur, India I. Sharma et al., 2015 [266]
Di-n-octyl phthalate (20) Memnoniella fungus culture medium GC/MS Melghat forest, Amravat, India H. Dilip et al., 2015 [267]
Di-n-octyl phthalate (20) Coleus foskohlii
(Plectranthus barbatus)
Perennial plant essential oil GC/MS India S. Takshak et al., 2016 [235]
Di-n-octyl phthalate (20) Aloe vera succulent plant leaf GC/MS Tamil Nadu, India T. Jeevitha et al., 2018 [88]
Di-n-octyl phthalate (20) Vernonia amygdalina (Asteraceae) leaf GC/MS Zaria, Nigeria S.S. Bello et al., 2018 [268]
Di-n-octyl phthalate (20) Alstonia boonei Deciduous tropical-forest tree stem bark GC/MS Okpuje, Enugu State, Nigeria A.A. Imam et al., 2017 [175]
Di-n-octyl phthalate (20) Canthium parviflorum Lam. (Plectoria parviflora) (Rubiaceae) callus, leaf GC/MS Andhra Pradesh,
India
S.C. Kala et al., 2017 [202]
Di-n-octyl phthalate (20) Astilbe chinensis (Saxifragaceae) volatile oil GC/MS China T. Yang et al., 2011 [96]
Di-octyl phthalate (20)****** Suaeda glauca Seepweeds, halophilic plants stem, leaf, root GC/MS Hulunbuir, China X. Lu et al., 2019 [269]
Di-octyl phthalate (20)****** Puccinellia tenuiflora Alkali grass (Poaceae) stem, leaf, root GC/MS Hulunbuir, China X. Lu et al., 2019 [269]
Di-octyl phthalate (20)****** Cyanthillium cinereum Perennial plant essential oil GC/MS Tamil Nadu
India
J. Dharani et al., 2018 [270]
Di-octyl phthalate (20)****** Rhizophora apiculata Mangrove plant leaf GC/MS Tamil Nadu
India
C.C.J. Paranjothi et al., 2018 [236]
Di-octyl phthalate (20)****** Brassica juncea L. Mustard plant leaf GC/MS Punjab, India A. Sharma et al., 2017 [203]
Di-n-propyl phthalate (22) Holoptelea integrifolia Indian elm leaf, stem, root GC/MS India A. Kavitha et al., 2014 [195]
Di-n-propyl phthalate (22) Astilbe chinensis (Saxifragaceae) volatile oil GC/MS China T. Yang et al., 2011 [96]
Di-n-propyl phthalate (22) Lysimachia microcarpa (Primulaceae) essential oil GC/MS China Z. Ding et al., 1993 [237]
Di-n-propyl phthalate (22) Lysimachia nummularia aurea (Primulaceae) essential oil GC/MS China J.F. Wei et al., 2013 [271]
Diundecyl phthalate (109) Hygrophila auriculata Medicinal plant
(Acanthaceae)
GC/MS Tiruchirapalli District, Tamil Nadu, India A.Z. Hussain et al., 2013 [272]
Diundecyl phthalate (109) Magnolia officinalis (Magnoliaceae) volatile oil GC/MS China Y. Lu et al., 2011 [273]
Isodecyl octyl phthalate (119) Trichoderma harzianum fungus GC/MS Nani, Allahabad, and Pipri, Faizabad, India A. Mishra et al., 2018 [194]
2-Ethyldecyl 2-ethylundecyl phthalate (97) Hippocampus kuda Bleeler seahorse whole body HRMS, MS, IR, 1H NMR, 13C NMR Zhoushan Island, Zhejiang, China Z.J. Qian et al., 2012 [173]
Y. Li et al., 2008 [152]
Ethyl heptyl phthalate
(120)
Curvularia senegalensis Filamentous fungus
(isolated from soil)
culture medium GC/MS Brazil E.M.F. Lucas et al., 2008 [108]
Ethyl 2-methylbutyl phthalate (121) Streptomyces cheonanensis VUK-A gram-positive bacterium (isolated from mangrove ecosystem) 1H NMR, 13C NMR, FT-IR, EI-MS Coringa, Gulf of Bengal, Andhra Pradesh U. Mangamuri et al., 2016 [246]
2-Ethylhexyl phthalate (MEHP, 26) Anabaena flos-aquae filamentous cyanobacterium GC/MS Different lo-calities, Taiwan B. Babu and J.-T. Wu, 2010 [212]
2-Ethylhexyl phthalate (MEHP, 26) Botryococcus braunii green algae GC/MS Different lo-calities, Taiwan B. Babu and J.-T. Wu, 2010 [212]
2-Ethylhexyl phthalate (MEHP, 26) Chlorella sp. single-celled green algae GC/MS Different lo-calities, Taiwan B. Babu and J.-T. Wu, 2010 [212]
2-Ethylhexyl phthalate (MEHP, 26) Cladophora fracta filamentous green algae GC/MS Different lo-calities, Taiwan B. Babu and J.-T. Wu, 2010 [212]
2-Ethylhexyl phthalate (MEHP, 26) Cylindrospermopsis raciborskii filamentous cyanobacterium GC/MS Different lo-calities, Taiwan B. Babu and J.-T. Wu, 2010 [212]
2-Ethylhexyl phthalate (MEHP, 26) Microcystis aeruginosa freshwater
cyanobacterium
GC/MS Different lo-calities, Taiwan B. Babu and J.-T. Wu, 2010 [212]
2-Ethylhexyl phthalate (MEHP, 26) Oscillatoria filamentous cyanobacterium GC/MS Different lo-calities, Taiwan B. Babu and J.-T. Wu, 2010 [212]
2-Ethylhexyl phthalate (MEHP, 26) Peridinium sp. marine dinoflagellate GC/MS Different lo-calities, Taiwan B. Babu and J.-T. Wu, 2010 [212]
2-Ethylhexyl phthalate (MEHP, 26) Peridinium bipes marine dinoflagellate GC/MS Different lo-calities, Taiwan B. Babu and J.-T. Wu, 2010 [212]
2-Ethylhexyl phthalate (MEHP, 26) Phormidium marine cyanobacterium GC/MS Different lo-calities, Taiwan B. Babu and J.-T. Wu, 2010 [212]
2-Ethylhexyl phthalate (MEHP, 26) Spirogyra sp. filamentous green algae (water silk) GC/MS Different lo-calities, Taiwan B. Babu and J.-T. Wu, 2010 [212]
2-Ethylhexyl phthalate (MEHP, 26) Trichoderma harzianum fungus GC/MS Nani, Allahabad, and Pipri, Faizabad, India A. Mishra et al., 2018 [194]
2-Ethylhexyl phthalate (MEHP, 26) Ligusticum porteri Apiaceae callus, aerial part, root GC/MS Chihuahua, Mexico, D. Goldhaber-Pasillas et al., 2012 [170]
2-Ethylhexyl phthalate (MEHP, 26) Telfairia
occidentalis Hook
Fluted pumpkin (Cucurbitaceae) seed GC/MS Uyo, Nigeria Eseyin et al., 2018 [248]
2-Ethylhexyl phthalate (MEHP, 26) Capsicum chinense Chili pepper
(Solanaceae)
Root exudate GC/MS China X. Han, et al., 2015 [238]
2-Ethylhexyl phthalate (MEHP, 26) Cupressus sempervirens Mediterranean cypress (Cupressaceae) bark and leaf GC/MS Al-Jabel Al-Akhdar Region, Libya M.E.I. Badawy et al., 2019 [239]
2-Ethylhexyl phthalate (MEHP, 26) Juniperus phoenicea Phoenicean juniper
(Cupressaceae)
Bark and leaf GC/MS Al-Jabel Al-Akhdar Region, Libya M.E.I. Badawy et al., 2019 [239]
2-Ethylhexyl phthalate (MEHP, 26) Sargassum wightii macro-algae IR, 1H NMR, 13C NMR Tuticorn, Tamil Nadu, India D. Rosaline et al., 2016 [274]
Isobutyl n-butyl phthalate (95) Cryptotaenia canadensis DC. Canadian honewort (perennial plant) Japan S. Hayashi et al., 1967* [158]
n-Nonyl n-propyl phthalate (115) Curvularia senegalensis Filamentous fungus
(isolated from soil)
culture medium GC/MS Brazil E.M.F. Lucas et al., 2008 [108]
Diheptyl phthalate (111) Aloe vera Succulent plant gel GC/MS Tochigi, Japan I. Yamaguchi et al., 1993 [275]
Diheptyl phthalate** (111) Lythrum salicaria Flowering plant whole plant GC/MS Sapporo, Japan E. Fujita et al., 1972 [200]
Dinonyl phthalate** (107) Lythrum salicaria Flowering plant whole plant GC/MS Sapporo, Japan E. Fujita et al., 1972 [200]
n-Octyl phthalate (28) Chorisia chodatii Floss silk tree
(Malvaceae)
flower UV-VIS, 1H NMR, 13C NMR; MS Minia University campus, Minia, Egypt J. Refaat et al., 2015 [276]
n-Octyl phthalate (28) Aloe vera Succulent plant gel GC/MS Tochigi, Japan I. Yamaguchi et al., 1993 [275]

Dialkyl phthalates are initially metabolized to monoalkyl phthalates by a number of microorganisms [104], and it has been realized that in the digestive lumen and liver of fish, monoalkyl phthalates (MPA) may also be produced from dialkyl phthalates [105]. This leads to 913 ± 885 ng/g MPA in European eel (Anguilla anguilla) muscles, collected in two French lagoons in the Mediterranean Sea [105], to 0.54 ng/g for benzyl phthalate (MBzP, 24) to 82 ng/g for n-butyl phthalate (MnBP, 25) in the muscles of juvenile Shiner Perch (Cymatogaster aggregata) [106] and to 0.24–1.1 ng/g for ethylhexyl phthalate (MEHP, 26, 6.63–60.9 ng/g for MnBP (25) in the white-spotted greenling (Hexagrammos stelleri) [107]. In these cases again, the substrate phthalates will be of anthropogenic origin. Monoalkyl phthalates such as MEHP (26) and MnBP (25) have been isolated from a number of bacteria, algae and fungi, but also from terrestrial plants (Table 2). Monoalkyl phthalates are being used as biomarkers for the original presence of dialkyl phthalates in organisms. The question remains in how far certain occurrences of phthalates in natural organisms indicate that they are natural products of these organisms. Table 2 shows a selection of reports of phthalates found in various organisms, especially in plants, bacteria, and fungi that do not specifically mention a possible anthropogenic origin of the phthalates. Of the 26 industrially most produced phthalates, only of diisoundecyl-, diisotridecyl- and of diallyl phthalate (3), no reports could be found regarding their isolation as products from plants. Interestingly, larger phthalates such as diisotridecyl phthalate, which is used in heat-resistant cables, have not been reported from plant isolates, either, yet. On the other hand, it would have been interesting to find the isolation of dialkyl phthalates that are known not to have been synthesized industrially. This data is hard to come by. Thus, it has been mentioned that one sign that bis(2-methylheptyl) phthalate were produced by Hypericum hyssopifolium (Guttiferae) itself, was that the compound was not used in the chemical industry [102]. It must be noted, however, that two patents existed for the production and use of the compounds at that time, one by BASF and one by Casio Computer Co [103].

It is interesting to screen the frequency of articles reporting on the isolation of phthalates with one short and one long alkyl chain, which is not that frequently found as additives in consumer products. These would include methyl propyl phthalate (57), n-butyl methyl phthalate (58), methyl n-pentyl phthalate (59), 2-ethylhexyl methyl phthalate (60) and the corresponding alkyl ethyl phthalates (Fig. 6). The interesting finding is that quite a few reports of isolation of these “mis-matched”, non-symmetric, less produced phthalates from different organisms exist [108]. n-Butyl n-tetradecyl phthalate (61) was isolated from the leaves of Urtica dioica L [109]. together with a number of other compounds of anthropogenic origin such as di-n-butylphthalate (DnBP, 5), di-2-ethylhexylphthalate (DEHP, 9), tributyl phosphate (55), and bis(2-ethylhexyl)maleate (56), all used as plasticizers, sealants or hydraulic fluids. Ethyl methyl phthalate (EMP, 23) was found in the stems of thorn apple [Datura stramonium L.] [110], in Italian thistle [Carduus pycnocephalus L.] [111], and dyer’s woad [Isatis indigotica] [112], among other plants. Research has shown that primary biodegradation of DEP mostly follows two paths, namely firstly the hydrolysis to monoethyl phthalate (MEP, 62) and then to phthalic acid (PA, 63) and secondly the de-methylation and trans-esterification to form ethyl methyl phthalate (EMP, 23). These pathways have been shown to operate in Pseudomonas sp. DNE-S1 [113] and in Sphingobium yanoikuyae SHJ [114]. Enzymatic trans-esterification in natural organisms of industrial phthalates to mixed phthalates should be considered but has not been studied, to the best of the author’s knowledge. Finally, phthalic acid has been found in a number of plant extracts, such as in the ethyl acetate extract of Bridelia ovata [115] and ethanolic extracts of licorice (Glycyrrhiza glabra) leaves [116], sometimes in concert with phthalates [117]. It must be noted, however, that phthalic acid (63) also can derive from the oxidation of naphthalenes as VOCs in the atmosphere. On the other hand, terephthalic acid (65) (see below) can derive from the burning of plastic, while 1,2,4-benzenetricarboxylic acid (64) can originate from the oxidation of polycyclic aromatic hydrocarbons (PAHs). Thus, phthalic acid, as well as terephthalic acid (65) and 1,2,4-benzenetricarboxylic acid (64), have been found residing on PM2.5 in the atmosphere (eg., at a max. of 73.2 ng/m3 collected air space over Nanhai, China; 178.5 ng/m3; and 43.4 ng/m3, respectively) [118].

As mentioned above, terephthalates, trimellitates and ring-hydrogenated analogs of phthalates, i.e., cyclohexane-1,2-dicarboxylates, have partially replaced phthalates as plasticizers in recent times, and they have started to appear in the environment in different concentrations. Thus, humans are equally exposed to terephthalates as has been shown in a recent German study on phthalate content in urine samples from 1999 to 2017, which indicated that the human exposure to para-phthalates (terephthalates) continues to grow [119] as these are replacing the phthalates as less regulated plasticizers. Here, the author tried to find whether this is also reflected in their isolation from natural sources. Indeed, reports on the isolation of terephthalates, especially from plant sources, could be found (Table 3), as could be on the isolation of isophthalates (dialkyl 1,3-phthalates, Table 4). Isophthalates in the form of ethylene terephthalate-isophthalate copolymers have been used in food packaging films, but have also been formulated as diluents in polymers such as polyethylene terephthalates [120]. Benzene-1,3-dicarboxylic acid (isophthalic acid, 66) has been isolated from a number of plants. Typical isolations have been reported from the essential oil of Dendrobium nobile [121], and stems of cultivated Dendrobium officinale, and Dendrobium huoshanense [122] (Orchidaceae), from the air-dried parts of the whole plant Swertia angustifolia (Gentianaceae) [123], from the leaves of Cerbera manghas (sea mango, Apocynaceae) [124], and from the culture filtrate of the yeast Candida tropicalis [125]. In addition, ring-substituted isophthalic acids have been found, such as 2-acetyl-5-hydroxy-4-methoxyisophthalic acid (67, Fig. 6) in the fungus Talaromyces flavus (Trichocomaceae) [126]. Few examples of the isolation of trimellitic acid esters as natural products could be located (Table 4), even though these also had been forwarded as additives to agrochemical powder preparations [127] such as to fertilizers [128]. Moreover, to date, no report could be found of the isolation of diisononyl cyclohexane-1,2-dicarboxylate from a plant or other organism as a natural product.

Fig. (6). Non-symmetric phthalates 57-61, ethyl phthalate 62, benzenedicarboxylic and tricarboxylic acids 63-67.

Table 3. Isolation of terephthalates from natural sources (organisms).
Terephthalate Organism Source Description of Organism Extracted Part of the Organism Identification Method of the Terephthalate Region/Location Reference
Bis-​(2-​ethylhexyl)​-​terephthalate (10) Melodinus fusiformis Plant (Apocynaceae) leaf, twig GC/MS China D. Wang et al, 2012 [198]
Bis-​(2-​ethylhexyl)​-​terephthalate (10) Grewia lasiocarpa E. Mey. ex
Harv.
Evergreen shrub GC/MS Umdoni Trust Park, KwaZulu-Natal, South Africa. N. Akwu et al., 2019 [277]
Bis-​(2-​ethylhexyl)​-​terephthalate (10) Uncaria rhynchophylla Plant (Cat’s claw herb) NMR, MS China (market purchased material) Y.-L. Wang et al., 2018 [231]
Bis-​(2-​ethylhexyl)​-​terephthalate (10) Penicillium griseofulvum Marine fungus China Y. Xu et al., 2015 [278]
Bis-​(2-​ethylhexyl)​-​terephthalate (10) Alnus nitida West Himalayan alder stem bark GC/MS Swat, Pakistan M. Sajid et al., 2017 [201]
Di-n-butyl terephthalate (4) Codonopsis thalictrifolia wall. var. mollis Soft bonnet bellflower MS China J. Jing et al., 2013 [279]
Di-n-butyl terephthalate (4) Semiaquilegia adoxoides Flowering plant (Ranunculaceae) roots NMR China N. Feng et al., 2006 [280]
Di-n-butyl terephthalate (4) Leucas zeylanica Ceylon slitwort
(Lamiaceae)
NMR, incl. 2D-NMR, MS Haikou, China N. Nidhal et al., 2020 [232]
Di-n-butyl terephthalate (4) Dalbergia cochinchinensis Thailand rosewood (Fabaceae) 1H NMR, 13C NMR Fangchenggang, Guangxi, China R. Liu et al., 2015
[199]
Di-n-butyl terephthalate (4) Melodinus hemsleyanus Plant (Apocynaceae) leaf, twig MS China J. Zhang et al., 2013 [281]
Di-n-butyl terephthalate (4) Incarvillea younghusbandii sprague Bignoniaceae China L. Shen et al., 2012 [282]
Di-n-butyl terephthalate (4) Dolomiaea souliei Flowering plant (Asteraceae) China H. Wei et al., 2012 [233]
Di-n-butyl terephthalate (4) Typhonium giganteum Engl. Chinese aroid essential oil China G. Peng, et al., 2010 [283]
Di-n-butyl terephthalate (4) Gynura divaricata Flowering medicinal plant (Asteraceae) aerial parts China L. Chen et al., 2010 [284]
Di-n-butyl terephthalate (4) Mosla chinensis Plant (Lamiaceae) China H. Liu et al., 2010 [285]
Diethyl terephthalate (8) Indigofera bungeana Plant ( Leguminosae) GC/MS China W. Tian et al., 2006 [286]
Diethyl terephthalate (8) Mangifera indica Plant (Anacardiaceae) NMR, MS Yunnan, China H. Jiang et al., 2019 [287]
Diisobutyl terephthalate (29) Radix paeoniae rubra
(Paeonia lactiflora Pallas and Paeonia veitchii Lynch)
Medicinal herb from perennial flowers (Paeoniacea) GC/MS China X. Feng et al., 2014 [288]
Diisobutyl terephthalate (29) Durian fruit (peel) tree volatile constituents of fruit peel GC/MS China B. Zhang et al., 2012 [192]
Di-n-octyl terephthalate (30) Elsholtzia communis Lamiaceae essential oil GC/MS China Y.L Lu et al., 2013 [289]
Dimethyl terephthalate* (18) Uncaria gambir (Roxb.) Flowering plant (Rubiaceae) leaf GC/MS West Sumatra, Indonesia D. Nandika et al., 2019 [290]
Dimethyl terephthalate* (18) Myristica argentea Papua nutmeg
(Myristicaceae)
NMR China J. Shi et al., 2010 [291]
Dimethyl terephthalate* (18) Elsholtzia communis Lamiaceae essential oil GC/MS China Y.L Lu et al., 2013 [289]
Dimethyl terephthalate* (18) Syzygium cumini Malabar plum (Myrtaceae) bark GC/MS Madhya Pradesh, India Mehta, B.K. et al., 2012 [211]
Dimethyl terephthalate* (18) Goniothalamus tapis Miq (Annonaceae) bark Malaysia B. Moharam et al., 2012 [292]
Dimethyl terephthalate* (18) Goniothalamus uvaroides King (Annonaceae) bark Malaysia B. Moharam et al., 2012 [292]
Dimethyl terephthalate* (18) Phoma
betae
Phoma
betae
Phoma
betae
Phoma betae (Pleospora betae)
Endophytic fungus plant pathogen fermentation extract State of São Paulo, Brazil M.B.C. Gallo et al., 2009 [293]
[4-(Methoxycarbonyl)-phenyl]methyl methyl terephthalate (31) Alnus nitida West Himalayan alder stem bark GC/MS Swat, Pakistan M. Sajid et al., 2017 [201]
Table 4. Isolation of isophthalates and trimellitates from natural sources (organisms).
Isophthalate and Trimellitate Organism Source Description of Organism Extracted Part of the Organism Identification Method of the Isophthalate Region/Location Reference
Tri(2-​ethylhexyl)​trimellitate (45) Marine bacteria from the sponge Acanthella cavernosa bacteria GC/MS Lombok, Indonesia T. Murniasih et al., 2016 [294]
Tri(2-​ethylhexyl)​trimellitate (45) Moringa oleifera Drumstick tree
(Moringaceae)
root GC/MS HEJICCBS garden, University of Karachi, Pakistan S. Faizi et al., 2014 [206]
Di-n-butyl isophthalate (46) Butia yatay Yatay palm Essential oil of the fruit GC/MS China Z.G. Lu et al., 2008 [295]
Di-n-butyl isophthalate (46) Elsholtxia fruticosa Rehd (Lamiaceae) Essential oil GC/MS China S.Z. Zheng et al., 2004 [296]
Di(ethylhexyl) isophthalate (48) Cordia myxa Flowering plant (Boraginaceae) leaf GC/MS Enrekang, South Sulawesi,
Indonesia
A. Najib et al., 2019 [297]
Di(ethylhexyl) isophthalate (48) Elaeagnus angustifolia Russian olive
(Elaeagnaceae)
Volatile oil of the flower GC/MS Xinjiang, China R. Aynur et al., 2015 [298]
Di(ethylhexyl) isophthalate (48) Capparis spinosa Caper bush
(Capparaceae)
Seed oil GC/MS Velenjak, Tehran, Iran K.M. Ara et al., 2014 [299]
Dioctyl isophthalate (47) Citrus maxima (Burm.) Merr. cv. Liangpin Yu Liangpin pomelo Pulp and skin
(exocarp)
GC/MS Market, China X. Bai et al., 2015 [300]
Dioctyl isophthalate (47) Zanthoxylum schinifolium Sichuan pepper GC/MS Market, China X. Bai et al., 2015 [300]
Dioctyl isophthalate (47) Pinctada martensii Pearl oyster Meat GC/MS China J. Liu et al., 2011 [301]
Dimethyl isophthalate (122) Syzygium cumini Malabar plum (Myrtaceae) bark GC/MS Ujjain (Madhya Pradesh), India B.K. Mehta et al., 2012 [211]

1.5. Uncommon Phthalates Isolated from Organisms as an Indication that These are Natural Products and not Products of Anthropogenic Origin

2-Methyl-, 2-ethyl, and 2-propylalkyl phthalates such as compounds 9, 21 36, and 43 exhibit stereocenter(s), where it must be noted that industrial phthalates are produced as stereoisomeric mixtures from the racemic alcohols. A number of papers have reported on the isolation of enantiopure or at least enantio-enriched phthalates [129, 130], indicating the natural origin of these phthalates. In the isolation of bis(2S-methylheptyl) phthalate (S-36) from the evergreen perennial plant Ajuga bracteosa, the authors did not forward any analytical result that indicated that the isolated substance was enantiopure or indeed chiral. The structure presented in the paper is that of the meso form of the compound, (R/S)-bis(2-methylheptyl) phthalate (36) [129], but the isolation of the compound could potentially be that of a mixture of stereoisomers. Different is the case of the isolation of bis(2S-methylheptyl) phthalate from Galinsoga parviflora, a herbaceous plant of the Asteraceae family, where the isolated compound shows a specific optical rotation [α]D23 of 193.5° (c = 0.075M, MeOH). Here, the question remains as to whether selective enzymatic hydrolysis of a mixture of bis(2-methylheptyl) phthalate stereoisomers has led to (R/S)-bis(2-methylheptyl) phthalate (36) as the one remaining dialkyl phthalate or whether the phthalate as a whole has been biosynthetically created (Fig. 7).

Undoubtedly, there are phthalates that have been isolated from organisms that thus far have had no place in the industry. One such is kurraminate [bis(2-hydroxymethylnonadec-3E-enyl) phthalate] (68) isolated from flowering plant Nepeta kurramensis at Khyber Pakhtunkhwa, Pakistan [131], along with known bis(2-ethyleicosyl) phthalate (33), which was also isolated from Phyllanthus muellerianus in West Africa [132]. Also, 33 is not produced industrially. Bis(7-acetoxy-2-ethyl-5-methylheptyl) phthalate (69) has been isolated from translucent honeysuckle (Lonicera quinquelocularis). This terminally hydroxylated phthalate, which possesses four stereocenters, not discussed by the authors, again is apparently not of anthropogenic origin [133, 134]. The phthalate has been isolated together with the common anthropogenic phthalates DEHP (9) and di-n-octyl phthalate (20). 69 shows an acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) inhibitory activity with IC50 of 1.65 and 5.98 μM.

One of the most compelling examples that phthalates can indeed be of natural origin is the isolation of a row of diethylene glycol phthalate ester oligomers from the marine-derived fungus Cochliobolus lunatus [135], which was subjected to epigenetic manipulation with the DNA transferase inhibitor 5-azacytidine (70). This led to the isolation of the seven diethylene glycol phthalate esters 72, 75-79, and 82 (Fig. 9), in addition to the known compounds 71, 74, 80, and 81 (Figs. 8 and 9). The compounds have been analyzed by NMR spectroscopic methods, and there is no question as to their identity. The fungus itself was obtained from a piece of fresh tissue from the inner part of the sea anemone Palythoa haddoni, collected from the Weizhou coral reef in the South China Sea [135]. The linear polyether motif is not common in nature. The central building block,​ bis[2-​(2-​hydroxyethoxy)​ethyl] phthalate (71), as an additive in polyurethanes, however, has been subject to a large number of patents [136, 137], appearing in patents as early as 1957 [138], and of directed synthesis [139]. [2-​(2-​Hydroxyethoxy)​ethyl] methyl phthalate (72) had not been reported previously, but [2-​(2-​hydroxyethoxy)​ethyl] phthalate (73) has been covered in a number of patents and also phthalate 74 has appeared in a patent [140].

A further strong indication that certain phthalates can be of natural origin comes from studies of C.Y. Chen et al., who showed with a 14C inclusion experiment that the red algae Bangia atropurpurea can de novo synthesize DEHP (9) and DnBP (5) [141]. B. atropurpurea filaments were cultured in a medium containing NaH14CO3. After two weeks, the radioactivity of DEHP (9) and DnBP (5) fractionated by HPLC from cultured filaments was analyzed, where single peak fractions of DEHP (160.00 cpm) and DnBP (4786.67 cpm) were found to have significantly higher radioactivities than the background (28.00 cpm) [141]. It is not clear, though, whether carbon-14 isotope was built into the structures indiscriminately or whether, for instance, it was only built into the alkyl chain of the esters.

Fig. (7). Phthalates 68 and 69, two phthalates that are not produced industrially.

Fig. (8). 5-Azacytidine (70), bis[2-​(2-​hydroxyethoxy)​ethyl] phthalate (71), [2-​(2-​hydroxyethoxy)​ethyl] methyl phthalate (72), [2-​(2-​hydroxyethoxy)​ethyl] phthalate (73) and bis-phthalate 74 [135].

Fig. (9). Diethylene glycol phthalate ester oligomers isolated from the marine-derived fungus Cochliobolus lunatus [135].

Looking at many of the known biosynthetic pathways involving aromatic structures such as the phenylpropanoid pathway, it is evident that these rarely give rise to aromatic substances with more than one carboxylic acid group substituting the arene unit. In fact, it is very uncommon to find an aromatic natural compound with two electron-withdrawing groups that is not an intermediate. More often than not, electron-donating hydroxyl, alkoxyl or amino groups are in evidence in naturally occurring aromatic compounds such as in the aromatic building blocks of plant lignins in the form of ferulates 83, hydroxycinnamates 84, with coniferyl alcohol (85) as a building block, in aromatic alkaloids such as bufotenin (86), flavonoids such as 2-phenylchromen-4-one (87), chalcones such as xanthohumol (88) and amino acids such tyrosine (89) and tryptophane (90) (Fig. 10).

C. Tian et al. showed that DnBP (5) is produced by naturally occurring filamentous fungi Penicillium lanosum PTN121, Trichoderma asperellum PTN7 and Aspergillus niger PTN42, cultured in an artificial medium [142]. Using an enzyme excreted by the fungi, the authors were able to enzymatically produce DnBP (5) under cell-free conditions from D-glucose (91) alone, from D-glucose and 1-butanol, from protocatechuic acid (94) and 1-butanol, and from phthalic acid (63) and 1-butanol (Fig. 11). This result indicates that DnBP (5) could be produced by the shikimic acid pathway [142], although the mechanism of the transformation of protocatechuic acid (94) to phthalic acid (63) is not clear, yet (Figs. 11-13).

Fig. (10). Typical natural products with an aromatic subunit.

Fig. (11). Proposed pathway from glucose (91) to dibutyl phthalate (5) [142].

Fig. (12). Butyl isobutyl phthalate (95) and 2,12-diethyl-11-methylhexadecyl 2-ethyl-11-methylhexadecyl phthalate (96) and 2-ethyldecyl 2-ethylundecyl phthalate (97), isolated from the seahorse Hippocampus Kuda Bleeler [152].

Fig. (13). Phthalates introduced in the tables.

1.6. Biological Activities of Phthalates Isolated from Organisms and Comparison to Activities and Hazard Assessment Associated with Industrial Phthalates

The biological assessment carried out on phthalates isolated from plants as potential natural products is quite different from that carried out on phthalates as industrial plasticizers. In the former, phthalates have been screened for their potentially benevolent effects such as antitumour compounds, antimicrobial products and larvicidal agents. In the latter, potential health and environmental risks associated with the compounds have been assessed, also for regulative purposes, which results, for instance, in the testing of these compounds for their hormonal activity. Both of these biological assessment series are nicely complementary.

In many reports of the isolation of phthalates from natural sources, the authors have tested plant extracts containing, apart from the phthalates, a plethora of other components. In these cases, it is difficult to tie the respective biological activity of the extract to the phthalate ingredient. However, there are also a number of reports of testing the biological activity of isolated phthalates collected from natural organisms. In this regard, bis(2-ethylhexyl)phthalate (9) isolated from the flower of Procera gigantea was found to be active against the gram-positive bacteria Staphylococcus aureus, Bacillus subtilis, Streptococcus equosemens and Sarcina lutea [143, 144] and against the gram-negative bacteria Closteridium perfringens, Escherchia coli, Pseudomonas aeruginosa, Shigella sonnei, Shigella shiga and Shigella dysenteriae [143, 144]. The compound was found to inactive against Bacillus megaterium [143]. Bis(2-ethylhexyl)phthalate (9) showed activity against the fungus Aspergillus flavus as well. Aspergillus fumigatus, Aspergillus niger, and Fusarium sp. were found to be resistant against the compound [143]. Not all biological activity tests have led to unanimous results, nevertheless a more detailed compilation of the antimicrobial test results of isolated and purified phthalates from the literature can be found in Table 5.

Both di-n-hexyl phthalate (14) and bis(2-propylheptyl) phthalate (21), isolated from the rhizopheric soil of the tobacco plant, have been found to have allelochemical properties versus lettuce (Lactuca sativa). Also, they showed autotoxic effects on the flue-cured tobacco plant itself [145] (Table 6). Allelochemical properties of phthalates are not unusual. Thus, dimethyl phthalate has been found to be a typical allelochemical of the perennial invasive plant Solidago canadensis (Canadian goldenrod) [146], which leads to delayed seed germination and reduced seedling growth of a number of plants such as wheat and mulberry. Dibutyl phthalate (DnBP, 5) and diisobutyl phthalate (DIBP, 12) were detected in high concentrations in naturally decomposed cotton stalk extracts. These strongly inhibited the cotton seedling growth in a bioassay, indicating autotoxic effects [147]. However, it must be noted that in all the cases above, it was not ascertained that the phthalates were indeed authentic natural products of the plants; also, it must be observed that such allelopathic effects should be taken into account when applying plastic mulch in plant production.

M. Uyeda et al. showed that DEHP (9) aggregates the gram-negative bacteria Proteus vulgaris and Serratia marcescens as well as HeLa cells [148]. Butyl isobutyl phthalate (95), this time isolated from the brown alga Laminaria japonica (Saccharina japonica), showed non-competitive inhibitory in vitro activity against α-glucosidase [149], toted at one time as a possible drug to help treat type II diabetes. Di-n-octyl phthalate (20) found in the plant Pachygone ovata (Poir.) Miers ex Hook. F. & Thomson is most likely of anthropogenic origin. The tests conducted with the isolated compound once again show the acute biological activity of such environmental pollutants. Di-n-octyl phthalate (20) was found to be cytotoxic towards MCF-7 breast cancer cells with an IC50 of 42.5 μg/mL. The compound was found to upregulate CASPASEs 3 and 9 and downregulate BCL2 gene expression, inducing BCL2 regulated apoptosis [150]. Dioctyl phthalate, here isolated from Nigella glandulifera Freyn, was also identified as a tyrosinase inhibitor, which leads to an inhibition of melanogenesis [151]. Other phthalates were found to be cytotoxic to MCF-7 (see Table 7).

Finally, the four phthalates, bis(2-ethylheptyl) phthalate (35), 2,12-diethyl-11-methylhexadecyl 2-ethyl-11-methylhexa- decyl phthalate (96), 2-ethyldecyl 2-ethylundecyl phthalate (97), and bis(2-ethyldodecyl) phthalate (34) isolated from the seahorse Hippocampus Kuda Bleeler, showed dose-dependent cathepsin B inhibition activities with IC50 values of 0.13 mM (1), 0.21 mM (2), 0.18 mM (3), and 0.29 mM (4), respectively [152]. Cathepsin B is a lysosomal cysteine protease of the papain family, which functions in intracellular protein catabolism.

Table 5. Antimicrobial activity of purified phthalates isolated from natural sources.
Antimicrobial Activity Phthalate Organism Source Part Extracted Reference
Staphylococcous aureus Bis(2-ethylhexylphthalate) (9) Calotropis gigantea flower M.R. Habib and M.R. Karim, 2009 [143]
S. aureus Bis(2-ethylhexylphthalate) (9) Streptomyces mirabilis broth extract M. El-Sayed, 2012 [144]
S. aureus Bis(2-ethylhexylphthalate) (9) Streptomyces sp. TN17 broth extract S. Smaoui et al., 2011 [302]
S. aureus / MIC 32 μg/mL Bis(2-ethylhexyl) phthalate (9) Streptomyces bangladeshiensis M.A.A. Al-Bari et al., 2006 [303]
S. aureus 209P FDA /MIC >300 μg/mL Di-n-butyl phthalate (5) Streptomyces nasri H35 Broth extract M.Y. El-Naggar, 1997 [214]
S. aureus NRRL B 313 Bis(2-ethylhexylphthalate) (9) Streptomyces SB9 Broth extract D. Lyutskanova et al., 2009 [304]
S. aureus MTCC 96/ MIC 18.75 μg/mL Bis(2-ethylhexylphthalate) (9) Brevibacterium McBellneri M. Rajamanikyam et al., 2017 [164]
S. aureus MTCC 96/ MIC 37.5 μg/mL Di-n-butyl phthalate (5) Brevibacterium McBellneri M. Rajamanikyam et al., 2017 [164]
Staphylococcus epidermis MTC 435 /MIC 9.37 μg/mL Bis(2-ethylhexylphthalate) (9) Brevibacterium McBellneri M. Rajamanikyam et al., 2017 [164]
Staphylococcus epidermis MTC 435 /MIC 9.37 μg/mL Bis(2-ethylhexylphthalate) (9) Brevibacterium McBellneri M. Rajamanikyam et al., 2017 [164]
Acinetobacter johnsonii ATCC17909 Bis(2-ethylhexylphthalate) (9) Streptomyces SB9 Broth extract D. Lyutskanova et al., 2009 [304]
Aeromonas hydrophila 2 μg/mL Bis(2-ethylhexylphthalate) (9 Streptomyces ruber EKH2 K.M. Barakat and E.A. Beltagy, 2015 [305]
Bacillus mycoides DSMZ274 (resistant) Bis(2-ethylhexylphthalate) (9) Streptomyces SB9 Broth extract D. Lyutskanova et al., 2009 [304]
Bacillus subtilis MIC 32 μg/mL Bis(2-ethylhexylphthalate) (9) Calotropis gigantea flower M.R. Habib and M.R. Karim, 2009 [143]
B. subtilis Bis(2-ethylhexylphthalate) (9) Vicia villosa shoots M.T. Islam et al., 2013 [181]
B. subtilis Bis(2-ethylhexylphthalate) (9) Streptomyces mirabilis broth extract M. El-Sayed, 2012 [144]
B. subtilis Diethyl phthalate (7) Vicia villosa shoots M.T. Islam et al., 2013 [181]
B. subtilis MTCC 441 /MIC 37.5 μg/mL Bis(2-ethylhexylphthalate) (9) Brevibacterium McBellneri M. Rajamanikyam et al., 2017 [164]
B. subtilis MTCC 441 /MIC 18.75 μg/mL Di-n-butyl phthalate (5) Brevibacterium McBellneri M. Rajamanikyam et al., 2017 [164]
B. subtilis 6633 ATCC /MIC >400 μg/mL Di-n-butyl phthalate (5) Streptomyces nasri H35 Broth extract M.Y. El-Naggar, 1997 [214]
B. subtilis 6633 Bis(2-ethylhexylphthalate) (9) Streptomyces SB9 Broth extract D. Lyutskanova et al., 2009 [304]
B. subtilis 6633 / MIC 84 μg/mL Di-n-butyl phthalate (5) Streptomyces albidoflavus N. Roy et al., 2006 [217]
B. subtilis / MIC 16 μg/mL Bis(2-ethylhexyl) phthalate (9) Streptomyces bangladeshiensis M.A.A. Al-Bari et al., 2006 [303]
Bacillus cereus PX MU-COB / MIC >300 μg/mL Di-n-butyl phthalate (5) Streptomyces nasri H35 Broth extract M.Y. El-Naggar, 1997 [214]
Bacillus megatherium (resistant) Bis(2-ethylhexyl) phthalate (9) Calotropis gigantea flower M.R. Habib and M.R. Karim, 2009 [143]
Bacillus megatherium NRRL 1353895 Bis(2-ethylhexyl) phthalate (9) Streptomyces SB9 Broth extract D. Lyutskanova et al., 2009 [304]
Closteridium perfringens Bis(2-ethylhexyl) phthalate (9) Streptomyces mirabilis broth extract M. El-Sayed, 2012 [144]
Salmonella typhi 653 / MIC 76 μg/mL Di-n-butyl phthalate (5) Streptomyces albidoflavus N. Roy et al., 2006 [217]
S. typhi / MIC 16 μg/mL Bis(2-ethylhexyl) phthalate (9) Streptomyces bangladeshiensis M.A.A. Al-Bari et al., 2006 [303]
Sarcina lutea / MIC 32 μg/mL Bis(2-ethylhexyl) phthalate (9) Calotropis gigantea flower M.R. Habib and M.R. Karim, 2009 [143]
Sarcina lutea ATCC9341 Bis(2-ethylhexyl) phthalate (9) Streptomyces SB9 Broth extract D. Lyutskanova et al., 2009 [304]
Edwardsiella tarda 8 μg/mL Bis(2-ethylhexyl) phthalate (9) Streptomyces ruber EKH2 K.M. Barakat and E.A. Beltagy, 2015 [305]
Escherchia coli Bis(2-ethylhexyl) phthalate (9) Calotropis gigantea flower M.R. Habib and M.R. Karim, 2009 [143]
E. coli Bis(2-ethylhexyl) phthalate (9) Streptomyces mirabilis broth extract M. El-Sayed, 2012 [144]
E. coli ATCC 8739 (resistant) Bis(2-ethylhexyl) phthalate (9) Streptomyces sp. TN17 broth extract S. Smaoui et al., 2011 [302]
E. coli MTCC 443 / MIC 37.5 μg/mL Bis(2-ethylhexyl) phthalate (9) Brevibacterium McBellneri M. Rajamanikyam et al., 2017 [164]
E. coli MTCC 443 / MIC 37.5 μg/mL Di-n-butyl phthalate (5) Brevibacterium McBellneri M. Rajamanikyam et al., 2017 [164]
E. coli 25922 / MIC 53 μg/mL Di-n-butyl phthalate (5) Streptomyces albidoflavus broth extract N. Roy et al., 2006
Klebsiella pneumoniae
(MTCC 618) / MIC 75 μg/mL
Bis(2-ethylhexyl) phthalate (9) Brevibacterium McBellneri M. Rajamanikyam et al., 2017 [164]
Klebsiella pneumoniae
(MTCC 618) / MIC 75 μg/mL
Di-n-butyl phthalate (5) Brevibacterium McBellneri M. Rajamanikyam et al., 2017 [164]
Micrococcus luteus Bis(2-ethylhexyl) phthalate (9) Streptomyces sp. TN17 broth extract S. Smaoui et al., 2011 [302]
Pseudomonas aeruginosa Bis(2-ethylhexyl) phthalate (9) Streptomyces mirabilis broth extract M. El-Sayed, 2012 [144]
P. aeruginosa MTCC 741 / MIC 75 μg/mL Bis(2-ethylhexyl) phthalate (9) Brevibacterium McBellneri M. Rajamanikyam et al., 2017 [164]
P. aeruginosa MTCC 741 / MIC 37.5 μg/mL Di-n-butyl phthalate (5) Brevibacterium McBellneri M. Rajamanikyam et al., 2017 [164]
P. aeruginosa 8 μg/mL Bis(2-ethylhexylphthalate) (9 Streptomyces ruber EKH2 broth extract K.M. Barakat and E.A. Beltagy, 2015 [305]
Pseudomonas fluores-cens / MIC >300 μg/mL Di-n-butyl phthalate (5) Streptomyces nasri H35 broth extract M.Y. El-Naggar, 1997 [214]
Shigella sonnei Bis(2-ethylhexyl) phthalate (9) Calotropis gigantea flower M.R. Habib and M.R. Karim, 2009 [143]
Shigella shiga Bis(2-ethylhexyl) phthalate (9) Calotropis gigantea flower M.R. Habib and M.R. Karim, 2009 [143]
Shigella dysenteriae Bis(2-ethylhexyl) phthalate (9) Calotropis gigantea flower M.R. Habib and M.R. Karim, 2009 [143]
S. dysenteriae / MIC 32 μg/mL Bis(2-ethylhexyl) phthalate (9) Streptomyces bangladeshiensis M.A.A. Al-Bari et al., 2006 [303]
Rhizobium vitis Bis(2-ethylhexyl) phthalate (9) Vicia villosa shoots M.T. Islam et al., 2013 [181]
R. vitis Diethyl phthalate (7) Vicia villosa shoots M.T. Islam et al., 2013 [181]
Streptococcus equosemens Bis(2-ethylhexyl) phthalate (9) Streptomyces mirabilis broth extract M. El-Sayed, 2012 [144]
Vibrio ordalii Bis(2-ethylhexylphthalate) (9 Streptomyces ruber EKH2 broth extract K.M. Barakat and E.A. Beltagy, 2015 [305]
Aspergillus flavus Bis(2-ethylhexyl) phthalate (9) Calotropis gigantea flower M.R. Habib and M.R. Karim, 2009 [143]
A. flavus (rel. resistant) Bis(2-ethylhexyl) phthalate (9) Streptomyces mirabilis broth extract M. El-Sayed, 2012 [144]
A. flavus / MIC 128 μg/mL Bis(2-ethylhexyl) phthalate (9) Streptomyces bangladeshiensis broth extract M.A.A. Al-Bari et al., 2006 [303]
Aspergillus fumigatus
(resistant)
Bis(2-ethylhexyl) phthalate (9) Calotropis gigantea
Streptomyces mirabilis
flower
broth extract
M.R. Habib and M.R. Karim, 2009 [143]
M. El-Sayed, 2012 [144]
A. fumigatus Di-n-butyl phthalate (5) Streptomyces nasri H35 Broth extract M.Y. El-Naggar, 1997 [214]
Aspergillus niger
(resistant)
Bis(2-ethylhexyl) phthalate (9) Calotropis gigantea
Streptomyces mirabilis
flower
broth extract
M.R. Habib and M.R. Karim, 2009 [143]
M. El-Sayed, 2012 [144]
A. niger 1781 / MIC 98 μg/mL Di-n-butyl phthalate (5) Streptomyces albidoflavus broth extract N. Roy et al., 2006 [217]
A. niger / MIC 64 μg/mL Bis(2-ethylhexyl) phthalate (9) Streptomyces bangladeshiensis broth extract M.A.A. Al-Bari et al., 2006 [303]
Curvularia pallescens 403 / 117 μg/mL Di-n-butyl phthalate (5) Streptomyces albidoflavus broth extract N. Roy et al., 2006 [217]
Fusarium sp. Bis(2-ethylhexyl) phthalate (9) Streptomyces sp. TN17 broth extract S. Smaoui et al., 2011 [302]
Fusarium sp.
(resistant)
Bis(2-ethylhexyl) phthalate (9) Calotropis gigantea flower M.R. Habib and M.R. Karim, 2009 [143]
Trichosporon cutaneum R57 Bis(2-ethylhexyl) phthalate (9) Streptomyces SB9 broth extract D. Lyutskanova et al., 2009 [304]
Candida albicans Bis(2-ethylhexyl) phthalate (9) Streptomyces mirabilis broth extract M. El-Sayed, 2012 [144]
C. albicans / MIC 64 μg/mL Bis(2-ethylhexyl) phthalate (9) Streptomyces bangladeshiensis broth extract M.A.A. Al-Bari et al., 2006 [303]
Candida tropicalis ATCC20336 Bis(2-ethylhexyl) phthalate (9) Streptomyces SB9 broth extract D. Lyutskanova et al., 2009 [304]
Saccharomyces cerevisiae (resistant) Di-n-butyl phthalate (5) Streptomyces nasri H35 broth extract M.Y. El-Naggar, 1997 [214]
S. cerevisiae DSM70449 Bis(2-ethylhexyl) phthalate (9) Streptomyces SB9 broth extract D. Lyutskanova et al., 2009 [304]
S. cerevisiae 176 / MIC 92 μg/mL Di-n-butyl phthalate (5) Streptomyces albidoflavus broth extract N. Roy et al., 2006 [217]
Table 6. Allelopathic properties of purified phthalates isolated from natural sources.
Affected Plant Phthalate Natural Source of the Phthalate Source of the Phthalate Reference
Lactuca sativa Di-n-hexyl phthalate (14) Tobacco plant rhizopheric soil X. Ren et al., 2015 [145]
Tobacco plant (autotoxic) Di-n-hexyl phthalate (14) Tobacco plant rhizopheric soil X. Ren et al., 2015 [145]
Lactuca sativa Bis(2-propylheptyl) phthalate (21) Tobacco plant rhizopheric soil X. Ren et al., 2015 [145]
Tobacco plant (autotoxic) Bis(2-propylheptyl) phthalate (21) Tobacco plant rhizopheric soil X. Ren et al., 2015 [145]
Table 7. Cytostatic activity of phthalates isolated from natural sources.
Cell Type and IC50 Value Phthalate Natural Source of the Phthalate Extracted Part of the Organism Reference
CHO (ATCC; CCL-61) IC50 = 36±8.6 μg/mL Di-n-butyl phthalate (5) Streptomyces albidoflavus broth extract N. Roy et al., 2006 [217]
CHO (ATCC; CCL-61) IC50 = 193±5.4 μg/mL Bis(2-ethylhexyl) phthalate (9) Streptomyces albidoflavus broth extract N. Roy et al., 2006 [217]
DU145 (ATCC; HTB-81) IC50 = 31.23±8.7 μg/mL Di-n-butyl phthalate (5) Streptomyces albidoflavus broth extract N. Roy et al., 2006 [217]
DU145 (ATCC; HTB-81) IC50 = 33.46±7.7 μg/mL Bis(2-ethylhexyl) phthalate (9) Streptomyces albidoflavus broth extract N. Roy et al., 2006 [217]
HEK293 (ATCC; CRL-
1573) IC50 = 19.77±10 μg/mL
Di-n-butyl phthalate (5) Streptomyces albidoflavus broth extract N. Roy et al., 2006 [217]
MCF-7 (ATCC; HTB-22) IC50 = 32.43±3.6 μg/mL Di-n-butyl phthalate (5) Streptomyces albidoflavus broth extract N. Roy et al., 2006 [217]
MCF-7 IC50 = 0.13 mM Di-n-octyl phthalate (20) Pachygone ovata (Poir.) Miers L.E. Amalarasi and G.J. Jothi, 2019 [150]
MCF-7 (ATCC; HTB-22) IC50 = 46.55±0.1 μg/ml Bis(2-ethylhexyl) phthalate (9) Streptomyces albidoflavus broth extract N. Roy et al., 2006 [217]
MCF-7 IC50 = 69.2 μM Bis(2-methylheptyl) phthalate (36) Phyllanthus pulcher G. Bagalkotkar, 2007 [177]
Toxicity against brine shrimp Artemia salina larvae LC50 = 2800 μg/mL Bis(2-ethylhexyl) phthalate (9) Streptomyces ruber EKH2 broth extract K.M. Barakat and E.A. Beltagy, 2015 [305]

CONCLUSION

Phthalates have been isolated from a multitude of different natural sources. Oftentimes, the phthalates are isolated as a bouquet of different phthalates, sometimes in conjunction with siloxanes, which definitely are of anthropogenic origin. This tends to signalize that in most of the cases, the phthalates themselves are of anthropogenic origin. While it is known that phthalates can stem from contamination from laboratory equipment, most of the phthalates found in natural sources may originate from fertilizers, other agrochemicals, irrigation water, or by import through the atmosphere. On the other hand, there are a few phthalates found in nature that are not produced industrially. As these differ solely in their O-alkyl groups, it must be considered whether enzymatic esterification/trans-esterification, starting from anthropogenic phthalates, may play a role. Furthermore, few phthalates have been found in nature in which the aromatic core is substituted further. Nevertheless, it has been shown that carbon-14 is built into secreted phthalates by B. atropurpurea filaments when cultured in a medium containing NaH14CO3. While a detailed, clear, and plausible biogenetic route to phthalates, should they be natural products, has not yet been forwarded, it could be shown with a fungal enzyme that dibutyl phthalate could be produced from glucose, indicating that a natural shikimic acid pathway to phthalates may exist. As phthalates upon isolation from various sources were seen as natural products, many of the biological assays typically carried out on newly identified natural compounds were also performed on them, leading to the recognition of their antimicrobial activity. These tests nicely complement the mandatory tests carried out on them as plasticizers produced industrially on a large scale.

LIST OF ABBREVIATIONS

BBzP  =  n-Butyl benzyl phthalate (1)
BCP  = n-Butyl cyclohexyl phthalate(2)
DAP  = Diallyl phthalate(3)
DnBT  = Di-n-butyl terephthalate(4)
DnBP  = Di-n-butyl phthalate(5)
DBEP  = Dibutoxy ethyl phthalate(6)
DEP  = Diethyl phthalate (7)
DET  = Diethyl terephthalate (8)
DEHP  = Bis(2-ethylhexyl) phthalate (9)
DEHT  = Di(2-ethylhexyl) terephthalate (10)
DcHP  = Dicyclohexyl phthalate (11)
DiBP  = Diisobutyl phthalate (12)
DIDP  = Diisodecyl phthalate (13)
DIHP  = Di-n-hexyl phthalate (14)
DINP  = Diisononyl phthalate (15)
DIOP  = Diisooctyl phthalate (16)
DMP  = Dimethyl phthalate (17)
DMT  = Dimethyl terephthalate (18)
DNPP  = Dipentyl phthalate (diamyl phthalate)(19)
DnOP  = Di-n-octyl phthalate (20)
DPHP  = Bis(2-propylheptyl) phthalate (21)
DPP  = Di-n-propyl phthalate (22)
EMP  = Ethyl methyl phthalate (23)
HDPE  = High density polyethene
LDPE  = Low density polyethene
MBzP  = Benzyl phthalate (24)
MnBP  = n-Butyl phthalate (25)
MEHP  = Ethylhexyl phthalate (26)
MnHP  = n-Hexyl phthalate (27)
MnOP  = n-Octyl phthalate (28)
MPA  = Monoalkyl phthalate
MW  = molecular weight
PVA  = Polyvinyl acetate
PVC  = Polyvinyl chloride

CONSENT FOR PUBLICATION

Not applicable.

STANDARDS OF REPORTING

PRISMA guidelines were followed in this study.

FUNDING

None.

CONFLICT OF INTEREST

The author declares no conflict of interest, financial or otherwise.

ACKNOWLEDGEMENTS

Declared none.

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