Gabriela Ramírez

Esaú Villatoro

Bogdan Ionescu

Hugo Jair Escalante

Sergio Escalera

Martha Larson

Henning Müller

Isabelle Guyon

Overview of the Multimedia Information Processing for Personality & Social Networks Analysis Contest

Keywords: Information fusion, personality analysis, social networks, handwritten recognition, multimedia information processing

Progress in the autonomous analysis of human behavior from multimodal information has lead to very effective methods able to deal with problems like action/gesture/activity recognition, pose estimation, opinion mining, user tailored retrieval, etc. However, it is only recently that the community has been starting to look into related problems associated with more complex behavior, including personality analysis, deception detection, among others. We organized an academic contest colocated with ICPR2018 running two tasks in this direction. On the one hand, we organized an information fusion task in the context of multimodal image retrieval in social media. On the other hand, we ran another task in which we aim to infer personality traits from written essays, including textual and handwritten information. This paper describes both tasks, detailing for each of them the associated problem, data sets, evaluation metrics and protocol, as well as an analysis of the performance of simple baselines.

Introduction

Computer Vision and Multimedia information processing are fruitful research fields that have focused on several tasks, among them the analysis of human behavior. Although great advances have been obtained in the so-called Looking at People field (see e.g., [START_REF] Escalera | Looking at people special issue[END_REF][START_REF]Visual Analysis of Humans -Looking at People[END_REF]), it has only been recently that attention from this area is targeting problems that have to do with more complex and subconscious behavior. For instance, personality and social behavior are only starting to be explored from computer vision and multimedia information processing perspectives [START_REF] Escalera | Guest editorial: Apparent personality analysis[END_REF]. This is the case due to a lack of data and benchmarks to evaluate such tasks.

Nevertheless, the availability of massive amounts of multimodal information together with the dominance of social networks as a fundamental channel where users interact have attracted the interest of the community in this direction of research. It should be noted that tools for effectively analyzing this behavior can have a major impact into everyone's life, with applications in health (e.g., support for mental disorders), security (e.g., forensics, preventive applications), human computer/machine/robot interaction (e.g., affective/interactive interfaces) and even entertainment (e.g., user-tailored systems).

We organize an academic contest collocated with the 2018 ICPR International Conference on Pattern Recognition 9 , comprising two tracks on the analysis of non-obvious human behavior from multimodal and social media data. On one hand we focus on information fusion for social image retrieval and diversification (DivFusion Task) using multimodal information obtained from social networks. This is a follow up of past challenges on diversification organized as part of the MediaEval Benchmarking Initiative for Multimedia Evaluation 10 . On the other hand, we organize the first competition on recognizing personality from digitized written documents (HWxPI Task). A new data set is released comprising in addition to images the transcripts of documents. With this track we aim to set the basis for research on inferring personality from user handwriting (including taking into account errors and the type of writing). Both tracks are at the frontier of research on Looking At People and multimedia information processing.

In this paper we describe the proposed tasks, the associated data sets and evaluation protocol in detail. Results obtained by baseline methods are reported and future work directions motivated by the contest are discussed.

The remainder of the paper is organized as follows. Section 2 describes the DivFusion task. Section 3 describes the HWxPI task. Section 4 outlines preliminary conclusions and future work directions.

DivFusion task

Overview

Diversification of image search results is now a hot research problem in multimedia. Search engines such as Google Image Search are fostering techniques that allow for providing the user with a diverse representation of search results, rather than providing redundant information, e.g., the same perspective of a monument or location. The DivFusion task builds on the MediaEval Retrieving Diverse Social Images Tasks that were addressing specifically the diversification of image search results in the context of social media. Figure 1 Participants receive a list of image search queries with up to 300 photos retrieved from Flickr and ranked with Flickr's default "relevance" algorithm 11 . The data are accompanied by various metadata and content descriptors. Each query comes also with a variety of diversification system outputs (participant runs from previous years), ranging from clustering techniques, greedy approaches, re-ranking, optimization and multi-system methods to human-machine-based or human-in-the-loop (i.e., hybrid) approaches. They are to employ fusion strategies to refine the retrieval results to improve the diversification performance of the existing systems even more.

The challenge reuses the publicly available data sets issued from the 2013-2016 MediaEval Retrieving Diverse Social Images tasks [START_REF] Ionescu | Div400: A social image retrieval result diversification dataset[END_REF][START_REF] Ionescu | Div150cred: A social image retrieval result diversification with user tagging credibility dataset[END_REF][START_REF] Ionescu | Div150multi: A social image retrieval result diversification dataset with multi-topic queries[END_REF][START_REF] Ionescu | Retrieving diverse social images at MediaEval 2016: Challenge, dataset and evaluation[END_REF], together with the participant runs. The data consist of hundreds of Flickr image query results (>600 queries, both single-and multi-topic) and include: images (up to 300 results images per query), social metadata (e.g., description, number of comments, tags, etc.), descriptors for visual, text, social information (e.g., user tagging credibility), as well as deep learning features, expert annotations for image relevance and diversification (i.e., clustering of images according to the similarity of their content). An example is presented in Figure 1. The data are accompanied by 180 participant runs that correspond to the output of various image search retrieval diversification techniques (each run contains the diversification of each query from a data set). These allow to experiment with different fusion strategies.

Data set

The data consist of a set of 672 queries and 240 diversification system outputs and is structured as following, according to the development -validationtesting procedure:

devset (development data): contains two data sets, i.e., devset1 (with 346 queries and 39 system outputs) and devset2 (with 60 queries and 56 system outputs); validset (validation data): contains 139 queries with 60 system outputs; testset (testing data): contains two data sets, i.e., seenIR data (with 63 queries and 56 system outputs, it contains the same diversification system outputs as in the devset2 data) and unseenIR data (with 64 queries and 29 system outputs, it contains unseen, novel diversification system outputs).

Overall the provided data consist of the following (which varies slightly depending on the data set, as explained below): images Flickr -the images retrieved from Flickr for each query; images Wikipedia -representative images from Wikipedia for each query; metadata -various metadata for each image; content descriptors -various types of content descriptors (text-visual-social) computed on the data; ground truth -relevance and diversity annotations for the images; diversification system outputs -outputs of various diversifications systems. For more information, see the challenge web page 12 .

Development data set Devset1 contains single-topic, location related queries.

For each location, the following information is provided: location name -is the name of the location and represents its unique identifier; location name query id -each location name has a unique query id code to be used for preparing the official runs; GPS coordinates -latitude and longitude in degrees; link to the Wikipedia web page of the location; a representative photo retrieved from Wikipedia in jpeg format; a set of photos retrieved from Flickr in jpeg format (up to 150 photos per location); an xml file containing metadata from Flickr for all the retrieved photos; visual and textual descriptors; ground truth for both relevance and diversity. Devset2 contains single-topic, location related queries.

For each location, the following information is provided: location name -is the name of the location and represents its unique identifier; location name query id -each location name has a unique query id code to be used for preparing the official; GPS coordinates -latitude and longitude in degrees; link to the Wikipedia web page of the location; up to 5 representative photos retrieved from Wikipedia in jpeg format; a set of photos retrieved from Flickr in jpeg format (up to 300 photos per location); an xml file containing metadata from Flickr for all the retrieved photos; visual, text and credibility descriptors; ground truth for both relevance and diversity.

Validation data set Contains both single-and multi-topic queries related to locations and events. For each query, the following information is provided: query text formulation -is the actual query formulation used on Flickr to retrieve all the data; query title -is the unique query text identifier, this is basically the query text formulation from which spaces and special characters were removed; query id -each location name has a unique query id code to be used for preparing the official runs; GPS coordinates -latitude and longitude in degrees (only for one-topic location queries); link to the Wikipedia web page of the query (when available); up to 5 representative photos retrieved from Wikipedia in jpeg format (only for one-topic location queries); a set of photos retrieved from Flickr in jpeg format (up to 300 photos per query); an xml file containing metadata from Flickr for all the retrieved photos; visual, text and credibility descriptors; ground truth for both relevance and diversity.

Test data set SeenIR data contains single-topic, location related queries. It contains the same diversification system outputs as in the devset2 data. For each location, the provided information is the same as for devset2. No ground truth is provided for this data. UnseenIR data contains multi-topic event related and general purpose queries. It contains unseen, novel diversification system outputs.

For each query, the following information is provided: query text formulationis the actual query formulation used on Flickr to retrieve all the data; query title -is the unique query text identifier, this is basically the query text formulation from which spaces and special characters were removed; query id -each query has a unique query id code to be used for preparing the official runs; a set of photos retrieved from Flickr in jpeg format (up to 300 photos per query); an xml file containing metadata from Flickr for all the retrieved photos; visual, text and credibility descriptors. No ground truth is provided for this data.

Ground truth The ground truth data consists of relevance ground truth and diversity ground truth. Ground truth was generated by a small group of expert annotators with advanced knowledge of the query characteristics. For more information on ground truth statistics, see the recommended bibliography on the source data sets [START_REF] Ionescu | Div400: A social image retrieval result diversification dataset[END_REF][START_REF] Ionescu | Div150cred: A social image retrieval result diversification with user tagging credibility dataset[END_REF][START_REF] Ionescu | Div150multi: A social image retrieval result diversification dataset with multi-topic queries[END_REF][START_REF] Ionescu | Retrieving diverse social images at MediaEval 2016: Challenge, dataset and evaluation[END_REF]. Relevance ground truth was annotated using a dedicated tool that provided the annotators with one photo at a time. A reference photo of the query could be also displayed during the process. Annotators were asked to classify the photos as being relevant (score 1), non-relevant (score 0) or with a "do not know" answer (score -1). A definition of relevance was available to the annotators in the interface during the entire process. The annotation process was not time restricted. Annotators were recommended to consult any additional information about the characteristics of the location (e.g., from the Internet) in case they were unsure about the annotation. Ground truth was collected from several annotators and final ground truth was determined after a majority voting scheme.

Diversity ground truth was also annotated with a dedicated tool. The diversity is annotated only for the photos that were judged as relevant in the previous step. For each query, annotators were provided with a thumbnail list of all the relevant photos. The first step required annotators to get familiar with the photos by analysing them for about 5 minutes. Next, annotators were required to re-group the photos into similar visual appearance clusters. Full size versions of the photos were available by clicking on the photos. A definition of diversity was available to the annotators in the interface during the entire process. For each of the clusters, annotators provided some keyword tags reflecting their judgments in choosing these particular clusters. Similar to the relevance annotation, the diversity annotation process was not time restricted. In this particular case, ground truth was collected from several annotators that annotated distinct parts of the data set.

Evaluation

Performance is assessed for both diversity and relevance. We compute Cluster Recall at X (CR@X) -a measure that assesses how many different clusters from the ground truth are represented among the top X results (only relevant images are considered), Precision at X (P@X) -measures the number of relevant photos among the top X results and F1-measure at X (F1@X) -the harmonic mean of the previous two. Various cut off points are to be considered, e.g., X=5, 10, 20, 30, 40, 50. Official ranking metrics is the CR@20. This metric simulates the content of a single page of a typical web image search engine and reflects user behavior, i.e., inspecting the first page of results in priority. Metrics are to be computed individually on each test data set, i.e., seenIR data and unseenIR data. Final ranking is based on overall mean values for CR@20, followed by P@20 and then F1@20.

Baseline

To serve as reference, each of the provided data sets is accompanied by a baseline system consisting of the Flickr initial retrieval results obtained with text queries. These are obtained with the Flickr's default relevance retrieval system. The testset baseline is also provided. It achieves the following performance: average metrics -CR=0.3514, P=0.6801, and F1=0.4410; metrics on SeenIR data -CR=0.3419, P=0.8071, F1=0.4699; metrics on UnseenIR data -CR=0.3609, P=0.5531, F1=0.4122.

Discussion

15 teams registered to the task but none of them managed to finish the competition by the deadline. One reason for this is the large and very rich data. Therefore, it is difficult to maneuver in the time alloted by the competition. Even though no system results were analysed, the provided evaluation data and tasks remain open and anyone interested in benchmarking fusion techniques can take advantage of this framework.

3 HWxPI task

Overview

According to Pennebaker, language is a good indicator of our personality, since through language one can express its way of thinking and feeling [START_REF] Pennebaker | The Secret Life of Pronouns: What Our Words Say About Us[END_REF]. The personality can be determined by stable patterns of behavior surfaced in any particular situation. In other words, the personality is defined by the characteristics that do not change, and that are independent of the situation in which a person is [START_REF] Vinciarelli | A survey of personality computing[END_REF]. Consequently, an automatic method can be use for extracting these patters in any production of a subject. In this fashion, using more views of the same subject can lead to identify complementary aspects of her or his personality.

In this task we aim to provide a standardized multimodal corpus for the personality identification problem. Particularly, the HWxPI task consists of estimating the personality traits of users from their handwritten texts and the corresponding transcripts. The traits correspond to the big five personality model used in psychology: extroversion, agreeableness, conscientiousness, emotional stability, and openness to experience.

The challenge comprises two phases: development and evaluation. For the first phase, the participants were encouraged to develop systems using a set of development pairs of handwritten essays (including image and text) from 418 subjects. Each subject has an associated class 1 and 0, corresponding to the presence of a strong or a weak presence of a specific personality trait. Thus, participants had to develop five binary classifiers to predict the pole of each trait.

For the final evaluation phase, an independent set of 293 unlabeled samples were provided to the participants. The provided predictions used the models trained on the development data.

The complete schedule of our challenge was managed through Codalab13 . Particularly, the first phase started February 20th and during the following three and a half month participants could follow their performance on the validation set. A total of 9 participants submitted predictions for the validation set. The final phase started on June 13th and same as in the previous phase, participant were able to see the results of their approach, this time, on the test set. For this phase, only two participants submitted predictions.

Data set

The corpus used in this task consists of handwritten Spanish essays from Mexican undergraduate students. A subset of this corpus and the gathering methodology is described in [START_REF] Ramírez-De-La-Rosa | TxPIu: A resource for personality identification of undergraduates[END_REF]. The textual modality is a transcription of the essays marked with seven tags of some handwritten phenomena: <D:description> (drawing), <IN> (insertion of a letter into a word), <MD> (modification of a word, that is a correction of a word), <DL> (elimination of a word), <NS> (when two words were written together; e.g., "Iam" instead of "I am") and, SB (syllabification).

The image modality was captured by scanner without edition of any type to the jpg file. Each pair of text plus image is labeled with the personality of its authors. Accordingly, the big five model of personality was used with traits: extroversion, agreeableness, conscientiousness, emotional stability, and openness to experience. Using the TIPI questionnaire [START_REF] Gosling | A very brief measure of the bigfive personality domains[END_REF] with answers of each subject, we could determine the class for each trait. The instrument provided a series of norms to decide the direction of each trait among four classes: high, medium high, medium low and low. For the HWxPI task, we binarize the classes to 1 for subjects with high and medium high and 0 for low and medium low traits.

The total number of instances in the corpus is 836, divided into three subsets: training, validation and test. The participants were given the training subset with the corresponding solution, the validation set was also available for tuning if necessary, while the test partition was used for the evaluation. The distribution of users (also referred to as subjects) per partition is shown in Table 1. And the information about the users per trait is shown in Table 2.

Finally, an example of a pair of image and text is given in Table 3. The image we provide has the complete letter sheet with considerable blank spaces.

Evaluation

We used Area under the ROC curve (AUC metric) to measure the performance of classification methods.

Baseline and preliminaries results

Since we have two modalities we use two baselines: one for text only and one for images only. For the first baseline (B_text) we preprocessed the transcriptions Table 3. Example of handwritten essay in Spanish, its manual transcription with added tags and its corresponding English translation Manual transcription Una vez sali <FO:salí> con un amigo no muy cercano, fuimos a comer y en la comida el chico se comportaba de forma extraña algo como <DL> desagradable <DL> <DL> con un <MD> aire de superioridad <MD> algo muy desagradable tanto para <DL> mi <FO:mí> como para las personas que estaban en nuestro alrededor pero ya despues <FO:después> cuando se dio cuenta de <DL> su comportamiento cambio <FO:cambió> la forma de como <FO:cómo> se portaba y fue muy humilde. English translation Once I went out with a friend not so close to me, we went to eat and while eating the guy was acting a little weird kind of rude as he was superior to me, it was rude for me as for the people around us but after he realized his behavior he changed the way he was acting and he was humble.

removing symbols and numbers. We keep the tags without the correction (for FO tag) without the description of the drawing (for the D tag). Then, we represented the text using character tri-grams with the TF weighting and an SVM classification.

For the second baseline (B_image) we relied on visual information only. We extracted histograms of oriented gradient (HoG) from the handwritten images and used them as input to the classification model. Nine bins and a cell size of 32 × 32 pixels was considered. SVM was used for classification.

Participant teams. During the development phase of our challenge we evaluated the methods of two participants over the validation set. The results per trait are shown in Figure 2. We can see that while the overall performance of the text baseline (B_text) is better than the participants, for some traits the participants performed better, particularly for agreeableness (agr in the figure) and openness (ope in the figure).

The first team called P_JR used the scanned image (visual information only) of the hand-written essay divided into patches and a convolutional neural network (CNN) as the classifier. From the 418 images in color in the train set, they obtained 216 patches of each scan in gray scale and then binarized them resulting in approximately 90,000 images. The CNN consists of five convolutional layers to extract features of the patches and 3 fully connected layers to perform the classification. The second team called P_EC used the transcriptions (text) by using a Bag of Words (BoW) and LIWC features for each subject representation. Then they concatenate these vectors with features extracted from the essay images (i.e., slant, size, space, etc.). The image features were extracted at character level, for the character segmentation task they trained a region proposal network over the EMNIST and Chars74k (handwritten) data sets. The features mentioned above were extracted using the character bounding box and the extreme points of the character contour.

For the final phase, results can be seen in Figure 3. Similar to the development, the average performance for the text baselines is slightly better than the results of the participants.

Discussion

Identifying a subject's personality given a small sample of handwritten text (transcriptions and/or images) is a very difficult task. We can see from the results of this challenge that relying only on the images can be useful to identify traits such as conscientiousness (con). Using only text from the transcriptions of each essay can help to identify emotional stability (sta) in both subsets as well.

As the results show, both participants have slightly lower performances than our baselines. However, the team called P_EC has a consistently better performance on openness. This team used a combination of both modalities (text and visual information). More experiments need to be done to determine the pertinence of use of both modalities for other traits.

Discussion

The two challenges describes in this paper make two large and interesting data sets available to the scientific community. Despite the limited participation the resources can clearly be useful in future research and with a longer time available to experiment this can lead to much more interesting results than in the short time available for the competition. Both resources will remain accessible for research and should help in the multimodal analysis of data about people, in this cases the need for diversity in the retrieval of images from social networks and on the detection of personality traits from handwritten texts.

  illustrates a diversification example from MediaEval 2015.

Fig. 1 .

 1 Fig. 1. Example of retrieval and diversification results for query "Pingxi Sky Lantern Festival" (to 14 results): (a) Flickr initial retrieval results; (b) diversification achieved with the approach from TUW [11] (best approach from MediaEval 2015).

Fig. 2 .

 2 Fig. 2. AUC performance for baselines (B_text and B_image) and participants (P_JR and P_EC) in the development phase of the challenge.

Fig. 3 .

 3 Fig. 3. AUC performance for baselines (B_text and B_image) and participants (P_JR and P_EC) in the final phase of the challenge.

Table 1 .

 1 Participants in the corpus divided by gender and average age per partition (train-validation-test).

	Partition Female Male Total
	Train	209 209 418
	Validation	125 293 293
	Test	59 66 125

Table 2 .

 2 Number of subjects by class per trait.

		Train Validation Test
	Trait	high low high low high low
	Openness	239 179 71	54 192 101
	Consciousness 171 247 61	64 137 156
	Extroversion	212 206 168 125 68 57
	Agreeableness 177 241 61	64 142 151
	Emot. Stability 186 232 73	52 148 145

http://www.icpr2018.org/.

https://www.flickr.com/services/api/.

https://competitions.codalab.org/competitions/18362

Acknowledgements

Gabriela Ramirez and Esaú Villatoro would like to thank the UAM-C for the facilities provided in this project. Their research was partially supported by CONACYT-Mexico under project grant 258588 and under the Thematic Networks program (Language Technologies Thematic Network, project 281795). Bogdan Ionescu's work was supported by the Romanian Ministry of Innovation and Research, UEFISCDI, project SPIA-VA, agreement 2SOL/2017, grant PN-III-P2-2.1-SOL-2016-02-0002. We would like also to acknowledge the contribution of the task co-organizers: Andrei Jitaru and Liviu Daniel Stefan, University Politehnica of Bucharest, Romania. Hugo Jair Escalante was supported by INAOE. Sergio Escalera's work has been partially supported by the Spanish project TIN2016-74946-P (MINECO/FEDER, UE) and CERCA Programme / Generalitat de Catalunya.


domain: sdu.ocean chim sde sdu

text:
Sopheak Net

Richard Sempeŕe

Anne Delmont

Andrea Paluselli

Baghdad Ouddane

Occurrence, Fate, Behavior and Ecotoxicological State of Phthalates in Different Environmental Matrices

Because of their large and widespread application, phthalates or phthalic acid esters (PAEs) are ubiquitous in all the environmental compartements. They have been widely detected throughout the worldwide environment. Indoor air where people spend 65-90% of their time is also highly contaminated by various PAEs released from plastics, consumer products as well as ambient suspended particulate matter. Because of their widespread application, PAEs are the most common chemicals that humans are in contact with daily. Based on various exposure mechanisms, including the ingestion of food, drinking water, dust/soil, air inhalation and dermal exposure the daily intake of PAEs may reach values as high as 70 μg/kg/day. PAEs are involved in endocrine disrupting effects, namely, upon reproductive physiology in different species of fish and mammals. They also present a variety of additional toxic effects for many other species including terrestrial and aquatic fauna and flora. Therefore, their presence in the environment has attracted considerable attention due to their potential impacts on ecosystem functioning and on public health. This paper is a synthesis of the extensive literature data on behavior, transport, fate and ecotoxicological state of PAEs in environmental matrices: air, water, sediment, sludge, wastewater, soil, and biota. First, the origins and physicochemical properties of PAEs that control the behavior, transport and fate in the environment are reviewed. Second, the compilation of data on transport and fate, adverse environmental and human health effects, legislation, restrictions, and ecotoxicological state of the environment based on PAEs is presented.

■ INTRODUCTION

PAEs are widely used in the manufacture and processing of plastic products as plasticizers. Production of PAEs began in the 1920s and has intensified since 1950, when these compounds were used to impart flexibility to polyvinyl chloride (PVC) resins. [START_REF] Kimber | An assessment of the ability of phthalates to influence immune and allergic responses[END_REF] To date, plasticizers are used in a very broad range of industrial applications. [START_REF] Simoneit | Combustion products of plastics as indicators for refuse burning in the atmosphere[END_REF][START_REF] Serodio | Considerations on ultra-trace analysis of phthalates in drinking water[END_REF] Not chemically but only physically bound to the polymeric matrix, PAEs can easily be released into the environment directly and/or indirectly, during manufacture, use, and disposal. [START_REF] Cadogan | An assessment of the release, occurrence and possible effect of plasticizers in the environment[END_REF] To date, PAEs are ubiquitous in the environment, including atmospheric aerosols, [START_REF] Xie | Occurrence and air-sea exchange of phthalates in the Arctic[END_REF][START_REF] Fu | Photochemical and other sources of organic compounds in the Canadian high Arctic aerosol pollution during winter-spring[END_REF] sludge from sewage and wastewater treatment, [START_REF] Dargnat | Phthalate removal throughout wastewater treatment plant: case study of Marne Aval station (France)[END_REF] river and marine waters/ sediments, [START_REF] Xie | Occurrence and air-sea exchange of phthalates in the Arctic[END_REF][START_REF] Net | Case study of PAHs, Me-PAHs, PCBs, phthalates and pesticides contamination in the Somme River water, France[END_REF] drinking water, [START_REF] Gao | Occurrence and fate of phthalate esters in full-scale domestic wastewater treatment plants and their impact on receiving waters along the Songhua River in China[END_REF] biota, and air. [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF][START_REF] Wang | Indoor phthalate concentration and exposure in residential and office buildings in Xi'an, China[END_REF] Some PAEs are endocrine disrupting chemicals, and their environmental behavior has attracted considerable attention due to their potential impact on ecosystem functioning and on public health. Consequently, six of them have been placed on the priority pollutant list of the United States Environmental Protection Agency (U.S. EPA), the European Union (EU), and on the list of priority pollutants in Chinese waters, [START_REF]Implementation of the Community Strategy for Endocrine DisruptersA Range of Substances Suspected of Interfering with the Hormone Systems of Humans and Wildlife[END_REF]14 and the concentrations of PAEs have been regulated for water consumption. The use of PAEs is now subject to stricter control and some have been prohibited or their reduction in numerous products has been recommended. A list of acronyms and abbreviations used in this review is provided in Table 1S in Supporting Information (SI).

I. Phthalates. I.1. Origin. Although di-n-butyl phthalate (DnBP) and di(2-ethylhexyl) phthalate (DEHP) can be synthesized by red algae [START_REF] Chen | Biosynthesis of di-(2-ethylhexyl) phthalate (DEHP) and di-n-butyl phthalate (DBP) from red alga-Bangia atropurpurea[END_REF] their natural origins are negligible compared with PAEs produced by human activities. Industrial use of PAEs that began in the 1930s is very broad on the worldwide scale. [START_REF] Schiedek | Impact of plasticizers (phthalic acid esters) on soil and groundwater quality[END_REF] To date, worldwide anual production of plastics has reached a level of 150 million tons, and 6-8 million tons of PAEs are consumed each year. European consumption of PAEs accounts for approximately 1 million tons. [START_REF] Mackintosh | Sorption of phthalate esters and PCBs in a marine ecosystem[END_REF][START_REF] Schreiber | Increasing and Confuidence in Detection When Analyzing Phthalates by LC-MS/MS[END_REF] The production of PAEs increased from 1.8 million tons in 1975 [START_REF] Peijnenburg | Occurrence of phthalate esters in the environment of the Netherlands[END_REF] to more than 8 million tons in 2011. [START_REF] Schreiber | Increasing and Confuidence in Detection When Analyzing Phthalates by LC-MS/MS[END_REF] PAEs are used in a very broad range of applications, [START_REF] Simoneit | Combustion products of plastics as indicators for refuse burning in the atmosphere[END_REF][START_REF] Serodio | Considerations on ultra-trace analysis of phthalates in drinking water[END_REF] and their content can be up to 10-60% by weight. [START_REF] Earls | Gas chromatographymass spectrometry determination of the migration of phthalate plasticisers from polyvinyl chloride toys and childcare articles[END_REF][START_REF] Van Wezel | Environmental risk limits for two phthalates, with special emphasis on endocrine disruptive properties[END_REF] PAEs are present in many materials or Table 1. Physicochemical Properties of Some PAEs Low molecular weight PAEs such as dimethyl phthalate (DMP), diethyl phthalate (DEP), and DnBP are components of industrial solvents, solvents in perfumes, adhesives, waxes, inks, pharmaceutical products, insecticide materials, and cosmetics. [START_REF] Koniecki | Phthalates in cosmetic and personal care products: concentrations and possible dermal exposure[END_REF] DMP and DEP allow perfume fragrances to evaporate more slowly, lengthening the duration of the scent, and a small amount of DnBP gives nail polish a chip-resistant property. PAEs with longer alkyl chains are used as plasticizers in the polymer industry to improve flexibility, workability, and general handling properties, and 80% of PAEs are used for this purpose. 23 The dispersion of PAEs in the environment can occur at all stages of their use, from their synthesis to their transformation or degradation.

I.2. Physicochemical Properties. A few key physicochemical properties including water solubility (S W ), vapor pressure (Vp), Henry's constant (H), air-water partitioning (K AW ), octanol-air partition (K OA ), and octanol-water partitioning (K OW ), organic carbon partitioning (K OC ) control both the behavior, transport and fate in the environment and also the exchanges between the different reservoirs such as atmosphere, lithosphere, hydrosphere, and biosphere. [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF]24,[START_REF] Cousins | Correlating the physical-chemical properties of phthalate esters using the 'three solubility' approach[END_REF] S W controls the distribution between water, soil/sediment, and atmosphere. Table 1 shows that S W of PAEs are low and decrease with the increase in the carbon chain length. K OW translates the affinity of an organic compound with the lipid molecules in living organisms. K OW has been used to predict the tendency of a contaminant to concentrate in aquatic organisms. 26 Log K OW increases with increasing alkyl chain length, indicating greater bioconcentration (Table 1). Vp declines more than 7 orders of magnitude with increasing alkyl chain length. Moreover, H indicates the tendency of a substance to escape from water into air. H can be calculated from Vp and S W . Compounds with H values ∼1.01 × 10 -2 Pa•m 3 /mol are generally considered to have negligible volatility. For higher alkyl chains ranging from 4 to 13 carbon atoms, H values range from 0.133 to 275 Pa•m 3 /mol which indicates that transfer from the aqueous phase to the gas phase is important (Table 1). K OC of PAEs range from 55 to 360 for DMP to 1.2 × 10 6 for ditridecyl phthalate (DTDP) in soil/ sediment and from 1020 for diisobutyl phthalate (DiBP) to 2 × 10 6 for di-n-octyl phthalate (DnOP) in suspended solids matter (SSM) (Table 1). K AW and K OA partition coefficients are among the key factors controlling the distribution of PAEs in different matrices in the environment. Log K AW and log K OA increase with the increasing alkyl chain length. High values of log K OA suggest that PAEs present in the atmosphere will be appreciably sorbed to aerosol particles and to soil and vegetation, whereas high values of log K AW suggest that PAEs potentially evaporate more rapidly from water. However, rapid evaporation from water could be mitigated by sorption to SSM in the water. [START_REF] Cousins | Correlating the physical-chemical properties of phthalate esters using the 'three solubility' approach[END_REF] The lower molecular weight PAEs are quite volatile and have very low log K AW values, so they will volatilize rapidly from the pure state but only very slowly from aqueous solution. [START_REF] Cousins | Correlating the physical-chemical properties of phthalate esters using the 'three solubility' approach[END_REF] II. Environmental Transport, Fate, Behavior. PAEs can be removed from environmental matrices by some processes that include microbiological transformation and degradation, volatilization, photo-oxidation, photolysis, sorption and biological uptake. [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF]24,27,[START_REF] Abdel-Daiem | Environmental impact of phthalic acid esters and their removal from water and sediment by different technologiesA review[END_REF] Field and laboratory studies have shown that aerobic or anaerobic microorganisms from various habitats (water, sediment, soil) are able to degrade PAEs. However, the half-lives of PAEs depend strongly on the condition of each habitat such as oxidant, microbial density, and sunlight irradiation.

Special attention should be focused on quality control/ assurance (QC/QA) when quantifying PAEs concentation in environmental matrices. Literature data showed that one of the main problems for PAEs analysis is the risk of contamination, as PAEs are ubiquitous and could be present in water, organic solvents, air, glassware and in the plastic material used for the analysis. The primary issue for the quantification of PAEs is not the trace analysis itself but the risk of contaminating the environmental samples during the analytical procedure, which can often lead to false positive or overestimated result. Thus, special attention should be focused on the quality controle and quality assurance when determined PAEs concentation. QC should be routinely implemented to minimize the risk of sample contamination. The blank should be free from any targeted PAEs to ensure that no significant contamination occurs during the whole procedure and ensure thus the reliable results. If PAEs are present at low concentrations, which account for less than a few % of those in the targeted sample, it is not necessary to subtract them from the sample measurement. However, if they are present at significant levels, they must be eliminated or subtracted from the sample measurement. [START_REF] Net | Reliable quantification of phthalates in environmental matrices (air, water, sediment, sludge and soil): A review[END_REF] II.1. Air. PAEs are ubiquitous in the atmosphere, including air indoors where people spend 65-90% of their time. [START_REF] Brasche | Daily time spent indoors in German homesBaseline data for the assessment of indoor exposure of German occupants[END_REF][START_REF] Hwang | Occurrence of endocrine-disrupting chemicals in indoor dust[END_REF] Indoor environments increase the lifetime of pollutants adsorbed to particles and dust by minimizing or eliminating the natural decomposition processes catalyzed by sunlight and rain. [START_REF] Cizdziel | Attics as archives for house infiltrating pollutants: trace elements and pesticides in attic dust and soil from southern Nevada and Utah[END_REF] Indeed, direct photolysis and photodegradation are major reaction pathways of PAEs responsible for PAE decay in the atmosphere. DEP and butyl cyclohexane phthalate (BCP) react photochemically with OH • with an estimated half-life of 22.2 and 23 h, respectively. [START_REF]Hazardous Substances Data Bank[END_REF] For DMP and DEHP, photolysis is important in the atmosphere where the indirect process of OH • attack predominates. The half-lifes of individual PAEs were estimated to be several days (see Supporting Information Table 4S) 3434 . Half-life of photo-oxidation of PAEs increases with the increasing alkyl chain length and OH • concentration. DnBP and DEHP have been used as softeners in water-based synthetic paintings, [START_REF] Orecchio | Determination of selected phthalates by gas chromatography-mass spectrometry in mural paintings from Palermo (Italy)[END_REF] so these compounds can be released into the atmosphere from painted surfaces [START_REF] Maertens | The mutagenic hazards of settled house dust: a review[END_REF] or photodegraded on mural painting surfaces under UV light irradiation in a dozen of hours (Supporting Information Table 4S). [START_REF] Barreca | Photodegradation of selected phthalates on mural painting surfaces under UV light irradiation[END_REF] On a mural painting, 68% of the total PAEs were degraded by irradiation only for a time period of 8 h.

PAEs can also be removed from the atmosphere by wet and dry deposition. PAEs with short carbon chains (<6) are present mainly in the gas phase, while PAEs with longer chains are mainly adsorbed on the particles. [START_REF] Wang | Indoor phthalate concentration and exposure in residential and office buildings in Xi'an, China[END_REF][START_REF] Teil | Atmospheric fate of phthalate esters in an urban area (Paris-France)[END_REF] Wet deposition is an important source of removal of short alkyl chains while dry deposition is an important source of removal of PAEs with long alkyl chains. Depositional fluxes of Σ 16 PAEs were estimated from 3.41 to 190 μg•m 2 /day for strong anthropogenic activity zones. This deposition process is initiated preliminarily by the association of PAEs with atmospheric particles. Among the 16 PAEs, DiBP, DnBP, and DEHP were the dominant ones. [START_REF] Zeng | Atmospheric deposition of phthalate esters in a subtropical city[END_REF] Atmospheric transport and deposition of PAEs can also be a significant process for their occurrence in soil and in the remote Atlantic and Arctic Oceans. The air-sea vapor exchange is an important process that intervenes in the mass balance of PAEs in the North Sea. [START_REF] Maertens | The mutagenic hazards of settled house dust: a review[END_REF][START_REF] Xie | Atmospheric concentrations and air-sea exchanges of phthalates in the North Sea (German Bight)[END_REF] The concentrations of PAEs were < n.d. to 3.4 ng/m 3 in the atmosphere and < n.d. to 6.6 ng/L in the water phase. The average of the air-sea exchange fluxes was estimated at -338 ng/m 2 /day for DnBP and -13 ng/m 2 /day for BBzP, suggesting a net deposition. However, the air-sea exchange fluxes of DEHP ranged from -95 to 686 ng/m 2 /day with average of 53 ng/m 2 /day, indicating that DEHP can be both deposited and volatilized from the surface water but volatilization is dominant. Volatilization and deposition process of PAEs in air-sea interface depend on the H. PAEs with low H values such as DnBP and BBzP were preferentialy deposited on sea surface, whereas DEHP with high H was dominated by volatilization. Air-sea exchanges of PAEs have also been estimated for the Norwegian, the Greenland, and the Arctic seas [START_REF] Xie | Occurrence and air-sea exchange of phthalates in the Arctic[END_REF] with total concentrations of 30-5030 pg/L and 1110-3090 pg/m 3 in the aqueous dissolved phase and the atmospheric gas phase, respectively. For DEHP, deposition dominated the air-sea gas exchange, while volatilization from seawater took place in the near-coast environment. The estimated net gas deposition of DEHP was 5, 30, and 190 tons per year for the Norwegian, the Greenland and the Arctic Seas, respectively, [START_REF] Xie | Occurrence and air-sea exchange of phthalates in the Arctic[END_REF] suggesting that atmospheric transport and deposition of PAEs is a significant process for their occurrence in the remote Atlantic and Arctic Oceans.

II.2. Water. PAEs can be accumulated in the hydrosphere via numerous processes, namely, atmospheric deposition, leaching, and drainage. [START_REF] Xie | Occurrence and air-sea exchange of phthalates in the Arctic[END_REF][START_REF] Xu | Occurrence and degradation characteristics of dibutyl phthalate (DBP) and di-(2-ethylhexyl) phthalate (DEHP) in typical agricultural soils of China[END_REF][START_REF] Zeng | Distribution of phthalate esters in urban soils of subtropical city, Guangzhou, China[END_REF][START_REF] Wang | Distributions of phthalic esters carried by total suspended particulates in Nanjing, China[END_REF] Hydrolysis of PAEs is negligible at neutral pH with aqueous hydrolysis half-lives in order of several years and up to more than 100 years for DnOP, DiOP and DEHP (see Supporting Information Table 4S). [START_REF] Wolfe | Phthalate ester hydrolysis: Linear free energy relationships[END_REF] UVB can penetrate surface water and induce photolysis of PAEs either directly by direct absorption of radiation or indirectly by the oxidation reactions of reactive chemical species such as OH

• , CO 3 -• , 1 O 2 , O 2 -•
, and chromophoric dissolved organic matter (CDOM) triplet states produced in surface waters by sunlight illumination of photoactive molecules (photosensitizers) such as nitrate, nitrite, and CDOM. [START_REF] Tedetti | Hydroxyl radical-induced photochemical formation of dicarboxylic acids from unsaturated fatty acid (oleic acid) in aqueous solution[END_REF][START_REF] Vione | Indirect photochemistry in sunlit surface waters: Photoinduced production of reactive transient species[END_REF] Under these conditions, aqueous half-lives of PAEs decrease considerably and ranging between 2.4 and 12 years and 0.12-1.5 years for DEP and DEHP, respectively. [START_REF] Wolfe | Use of linear free energy relationship and an evaluative model to assess the fate and transport of phthalate esters in the aquatic environment[END_REF] Under light irradiation, PAEs react with photogenerated OH • to form 4-hydroxy phthalate esters that present potential toxicity. 27 Biodegradation can be the most important process for the removal of PAEs from water. Indeed, PAEs can be accumulated and degraded rapidly by microorganism under both aerobic and anaerobic conditions. In surface waters (seawater or freshwater) under aerobic conditions excluding low temperatures (<5 °C) and poor nutritional conditions, the half-lives of primary degradation vary from less than 1 day to 2 weeks, and the halflives for complete mineralization are approximately 10 times longer. [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF] However, Cousins and Palm 47 have reported the water half-life of DEHP and DiNP at 360 and 900 h, respectively (Supporting Information Table 4S). The biodegradation of PAEs varies depending on the density and type of species. DEP was detected in aquatic organisms with a modest level, [START_REF] Camanzo | Organic priority pollutants in nearshore fish from 14 Lake Michigan tributaries and embayments[END_REF][START_REF] Devault | Contaminants in fish from Great Lakes harbors and tributary mouths[END_REF] and it is unlikely to biomagnify up the food chain because it is degraded by organisms. [START_REF] Epa | Health and Environmental Effects Profile for Phthalic Acid Esters[END_REF] The order of biodegradation of PAEs was algae <cnidarians <molluscs <crustaceans <fish. [START_REF] Wofford | Bioaccumulation and metabolism of phthalate esters by oysters, brown shrimp and sheephead minnows[END_REF] The half-life of DEP in fish tissue is 1-2 days. [START_REF] Barrows | Bioconcentration and elimination of selected water pollutants by bluegill sunfish (Lepomis macrochirus). In Dynamics, Exposure and Hazard Assessment of Toxic Chemicals[END_REF][START_REF] Veith | An Evaluation of Using Partition Coefficients and Water Solubility to Estimate Bioconcentration Factors for Organic Chemicals in Fish, Aquatic Toxicology[END_REF] Although DEHP can be volatilized from seawater in the near-coast environment, global tendencies suggest that deposition dominates the air-sea exchange of PAEs. [START_REF] Xie | Occurrence and air-sea exchange of phthalates in the Arctic[END_REF][START_REF] Xie | Atmospheric concentrations and air-sea exchanges of phthalates in the North Sea (German Bight)[END_REF] II.3. Sediment. Few studies have focused on the biodegradability of PAEs in river and marine sediment. The kinetics of anaerobic degradation of PAEs in river sediment depends on various factors including pH, temperature, surfactants, pollutants, or microbial inhibitors. Microbial action is thought to be the principal mechanism for PAEs degradation in both aquatic and terrestrial systems (e.g., sewage, soils, sediments, water). [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF]24 In mangrove sediments, under aerobic condition, the degradation half-lives of DnBP and DEHP were estimated to be only fews days (SI Table 4S). Similar half-lives of DEP, DnBP, and DEHP were found for river sediment under anaerobic conditions (30 °C with pH 7) [START_REF] Chang | Anaerobic degradation of diethyl phthalate, di-n-butylphthalate, and di-(2-ethylhexyl) phthalate from river sediment in Taiwan[END_REF] (Supporting Information Table 4S). For river sediment under anaerobic conditions, DnBP, DPhP, and BBzP might be degraded rapidly whereas DEP and DEHP degradation rates were very low. [START_REF] Yuan | Biodegradation of dibutyl phthalate and di-(2-ethylhexyl) phthalate and microbial community changes in mangrove sediment[END_REF][START_REF] Yuan | Occurrence and microbial degradation of phthalate esters in Taiwan river sediments[END_REF] Primary biodegradation rates in sediments were estimated at 3-4 weeks and 3 months, respectively, for DnBP and DEHP. [START_REF] Fish | Characteristics of various hydrosoils and their relative importance in the biodegradation of DEHP[END_REF][START_REF] Tegatz | Toxicity of dibutyl phthalate-contaminated sediment of laboratory-and field-colonized estuarine benthic communities[END_REF] Sediment half-life of DEHP and DiNP were estimated at less than 1 year 47 (Supporting Information Table 4S). Otton et al. [START_REF] Otton | Biodegradation of mono-alkyl phthalate esters in natural sediments[END_REF] measured the biodegradation kinetics of eight monoalkyl phthalate esters (MPEs) in marine and freshwater sediments collected from three locations in the Greater Vancouver area. The studied MPEs were degraded in both marine and freshwater sediments at 22 °C with half-lives ranging between 16 and 39 h. In marine sediments, half-lives of these eight MPEs were found in the ranges of 18 ± 4-35 ± 10 h, which is similar to the range of half-lives found in freshwater sediment (16 ± 2-39 ± 6 h). [START_REF] Otton | Biodegradation of mono-alkyl phthalate esters in natural sediments[END_REF] These results suggest that the half-life of PAEs increased strongly (ca. 8-fold) with temperatures in the range of 5-22 °C and did not depend on alkyl chain length.

II.4. Soil. Atmospheric deposition and sewage sludge used as soil amendment are the important sources of PAEs in soil, especially in agricultural areas. The most abundant PAEs in soil are DiBP, DnBP and DEHP, which represent 74.2-99.8% of ∑ 16 PAEs. [START_REF] Zeng | Distribution of phthalate esters in urban soils of subtropical city, Guangzhou, China[END_REF] In soil, the half-lives of PAEs vary from 1 to 75 days, much lower than the half-life found for polychlorobiphenyls (7-25 years) under the same conditions. [START_REF] Mackintosh | Sorption of phthalate esters and PCBs in a marine ecosystem[END_REF] DEP was not expected to persist in the environment with a degradation half-life in soil of approximately 0.75 days at 20 °C, whereas only 10% of DEHP was removed from the same soil after 70 days incubation. [START_REF] Cartwright | Degradation and impact of phthalate plasticizers on soil microbial communities[END_REF] However, more recently, Cousins and Palm [START_REF] Cousins | Physical-chemical properties and estimated environmental fate of brominated and iodinated organic compounds[END_REF] have reported the soil half-life of DEHP and DiNP at 30 and 75 days, respectively.

Depending on meteorological conditions, PAEs in soil can also contribute to water or atmospheric pollution by evaporation, leaching, deposition and drainage, [START_REF] Xu | Occurrence and degradation characteristics of dibutyl phthalate (DBP) and di-(2-ethylhexyl) phthalate (DEHP) in typical agricultural soils of China[END_REF][START_REF] Zeng | Distribution of phthalate esters in urban soils of subtropical city, Guangzhou, China[END_REF][START_REF] Wang | Distributions of phthalic esters carried by total suspended particulates in Nanjing, China[END_REF] consequently modifying their concentration and fate. Abiotic degradation experiments of DnBP and DEHP indicated that only 0.60-2.91% were degraded during 30 days which is much slower than their biodegradation, [START_REF] Xu | Occurrence and degradation characteristics of dibutyl phthalate (DBP) and di-(2-ethylhexyl) phthalate (DEHP) in typical agricultural soils of China[END_REF] depending on the type of soil. Half-lives of DnBP and DEHP were estimated at 7.8 ± 0.1 and 26.3 ± 0.7 days in black soil versus 8.3 ± 0.2 and 30.8 ± 0.7 days in fluvo-aquic soil likely due to the higher density of microorganisms in the former case. [START_REF] Xu | Occurrence and degradation characteristics of dibutyl phthalate (DBP) and di-(2-ethylhexyl) phthalate (DEHP) in typical agricultural soils of China[END_REF] III. Impact on Biosphere and Regulation. The toxicity of PAEs remains under debate because the debate is characterized by tension between the commercial importance of PAEs and their impact on human health and on the environment. However, a large variety of field and laboratory studies reveals high exposure and evident toxicity of PAEs affecting human health and other biospheres.

III.1. Human Exposure and Health Impact. For humans, the potential pathways for exposure to PAEs are inhalation, contaminated foodstuffs, drinking water or dermal contact with cosmetics containing PAEs. [START_REF] Koniecki | Phthalates in cosmetic and personal care products: concentrations and possible dermal exposure[END_REF][START_REF] Heudorf | Phthalates: Toxicology and exposure[END_REF][START_REF] Guo | Comparative assessment of human exposure to phthalate esters from house dust in China and the United States[END_REF] Thus, the study of PAEs in air, foodstuffs, drink and other products in human life has been paid more attention. [START_REF] Weschler | Indoor/outdoor connections exemplified by processes that depend on an organic compound's saturation vapour pressure[END_REF][START_REF] Das | Intake estimates of phthalate esters for South Delhi population based on exposure media assessment[END_REF][START_REF] Zhang | Phthalate esters (PAEs) in indoor PM 10 /PM 2.5 and human exposure to PAEs via inhalation of indoor air in Tianjin, China[END_REF] Concentration levels of some individual PAE in milk, drink and food are presented in Table 2S in Supporting Information. The concentrations of individual PAE were detected from not detected level to fews thousands ng/g dw and can be up to 24 μg/g dw in foods (DEHP in olive oil) and 215 μg/L in milk (Supporting Information Table 2S). The low molecular weight PAEs (DMP, DEP) were found at much lower levels compared to the high molecular weight PAEs and the highest was detected for DEHP (Supporting Information Table 2S). Total PAEs were detected in the range 0.133-3.804 μg/L in drinking water [START_REF] Das | Intake estimates of phthalate esters for South Delhi population based on exposure media assessment[END_REF][START_REF] Yang | Monitoring and removal of residual phthalate esters and pharmaceuticals in the drinking water of Kaohsiung City, Taiwan[END_REF] whereas ∑ 17 PAEs ranged from 0.29 to 23.77 μg/m 3 in indoor air and within 123-9504 μg/g in the dust phase. [START_REF] Wang | Indoor phthalate concentration and exposure in residential and office buildings in Xi'an, China[END_REF] High levels of PAEs were detected in indoor air where people spent 65-90% of their time. [START_REF] Brasche | Daily time spent indoors in German homesBaseline data for the assessment of indoor exposure of German occupants[END_REF][START_REF] Hwang | Occurrence of endocrine-disrupting chemicals in indoor dust[END_REF][START_REF] Cousins | Emissions of two phthalate esters and BDE 209 to indoor air and their impact on urban air quality[END_REF] The daily intake of six PAEs through air inhalation in indoor air has been estimated for infants, toddlers, children, teenagers and adults. [START_REF] Zhang | Phthalate esters (PAEs) in indoor PM 10 /PM 2.5 and human exposure to PAEs via inhalation of indoor air in Tianjin, China[END_REF] The total exposure doses were within the median daily intake of 155.850-664.332 ng/kg/day for ∑ 6 PAEs, and the highest level was detected in infants. The daily exposure to indoor PAEs in indoor air and dust was estimated to range from 2.6 μg/kg/day (for adults) to 7.4 μg/ kg/day (for toddlers). [START_REF] Wang | Indoor phthalate concentration and exposure in residential and office buildings in Xi'an, China[END_REF] Overall, from various exposure pathways based on ingestion of food, drinking water, dust/soil, air inhalation, oral and dermal exposure pathways, daily intake of DMP, DEP, DnBP, DiBP, BBzP, and DEHP has been estimated in the range of 0.08-69.58 μg/kg/day. [START_REF] Das | Intake estimates of phthalate esters for South Delhi population based on exposure media assessment[END_REF][START_REF] Clark | Modeling human exposure to phthalate esters: A comparison of indirect and biomonitoring estimation methods[END_REF] Food as the major contributor represents more than 67% of human exposure. [START_REF] Das | Intake estimates of phthalate esters for South Delhi population based on exposure media assessment[END_REF] Consequently, PAEs and their metabolites have been detected in the human body (i.e., breast milk, blood, urine). [START_REF] Liou | Monitoring of PAEMs and beta-agonists in urine for a small group ofexperimental subjects and PAEs and beta-agonists in drinking waterconsumed by the same subjects[END_REF][START_REF] Chen | Analysis of di-n-butyl phthalate and other organic pollutants in Chongqing women undergoing parturition[END_REF] In urine, metabolites of DnBP and DEHP were the main PAEs metabolites (PAEMs) detected. [START_REF] Liou | Monitoring of PAEMs and beta-agonists in urine for a small group ofexperimental subjects and PAEs and beta-agonists in drinking waterconsumed by the same subjects[END_REF] Urinary PAEMs concentrations did not depend on sexes but they depend significantly on age. [START_REF] Liou | Monitoring of PAEMs and beta-agonists in urine for a small group ofexperimental subjects and PAEs and beta-agonists in drinking waterconsumed by the same subjects[END_REF] The most frequently detected PAEs were reported to be DnBP and DEHP, found at highest levels in venous blood followed by breast milk, umbilical cord blood and urine; this order depends on metabolic factors. [START_REF] Chen | Analysis of di-n-butyl phthalate and other organic pollutants in Chongqing women undergoing parturition[END_REF] When ingested through contaminated food, PAEs are converted by intestinal lipases to MPE, suggesting that DEHP was converted to mono-2-ethylhexyl phthalate (MEHP), while DnBP and BBzP were converted to the toxic metabolite monobenzyl phthalate (MBzP). [START_REF] Main | Human breast milk contamination with phthalates and alterations of endogenous reproductive hormones in infants three months of age[END_REF][START_REF] Singh | Epigenetic effects of environmental chemicals bisphenol A and phthalates[END_REF] High levels of four urinary phthalate metabolites have been reported. [START_REF] Kolena | Phthalate exposure and health-related outcomes in specific types of work environment[END_REF] Blood, serum and urine are the general choice of biological matrixes to assess the level of PAEs and their metabolites exposure in human. However, hair is an alternative biological specimen. In urine, MnBP was found to be the highest, followed by the metabolites MEP, MEHP and MiNP with, respectively, 71.42 ± 90.19, 68.32 ± 43.74, 15.37 ± 20.09, and 1.47 ± 4.47 ng/mL. In epidemiological studies, DEHP has been associated with the development of wheezing and allergic airway diseases. [START_REF] Oie | Residential exposure to plasticizers and its possible role in the pathogenesis of asthma[END_REF][START_REF] Blanc | How much adult asthma can be attributed to occupational factors?[END_REF] Some PAEs are known to be toxic to the developing male reproductive system, and low-molecularweight PAEs have been found to cause irritation of eyes, nose and throat. [START_REF] Benson | Hazard to the developing male reproductive system from cumulative exposure to phthalate esters-dibutyl phthalate, diisobutyl phthalate, butylbenzyl phthalate, diethylhexyl phthalate, dipentyl phthalate, and diisononyl phthalate[END_REF] Some PAEs (DnBP, DEHP) and their metabolite (MBP) can cause serious to humain health. Given the high contributor of food (>67%) on human exposure, stricter controls should be adopted for food to minimize the effect of PAEs on human health.

However, despite the cited adverse effects, DEHP could be beneficial for the patients with glioblastoma multiforme. Exposure of glioblastoma cells to DEHP revealed a significant inhibition of cell migration and invasion and led to a significant reduction in cell proliferation. [START_REF] Sims | Di-ethylhexylphthalate (DEHP) modulates cell invasion, migration and anchorage independent growth through targeting S100P in LN-229 glioblastoma cells[END_REF] The main concerns related to exposure to PAEs in humans are the effects on reproduction, including fertility problems (effect of endocrine disruption), the development of newborns and carcinogenic character. [START_REF] Behnke | An aerosol smog chamber for testing abiotic degradation[END_REF] Howdeshell et al. [START_REF] Howdeshell | Mechanisms of action of phthalate esters, individually and in combination, to induce abnormal reproductive development in male laboratory rats[END_REF] have reported that when PAEs were mixed with other antiandrogenic compounds, the effect cumulative on male reproductive tract development when administered during sexual differentiation in utero, potentially affecting human reproductive development were observed.

III.2. Potential Environmental Risk. Numerous studies have focused on the ecotoxicology of PAEs in biota including aquatic organisms and rodents. The latter is useful to estimate the toxicity to humans. Compilation data of DnBP and DEHP showed that aquatic organisms can accumulate high levels of PAEs. [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF] More recently, Vethak et al. [START_REF] Vethaak | Oestrogens and Xeno-Estrogens in the Aquatic Environment of the Netherlands, Occurrence, potency and biological effectsRIZA/RIKS-report[END_REF] reported contamination of DEP and DEHP in freshwater species such as the bream at 1900-3120 μg/kg dw of DEHP and 720-800 μg/kg dw of DEP and for such marine species as the flounder, at 40-70 μg/ kg dw of DEHP and 100-200 μg/kg dw of DEP.

PAEs are involved in endocrine disrupting effects, namely, upon reproductive physiology in different species of fish and mammals. [START_REF] Harris | The estrogenic potential of phthalate esters in vitro[END_REF] They are also toxic for many other species: for DEP, LC50/EC50 values ranged from 3 mg/L (marine alga) to 132 mg/L (protozoan), with the lowest NOECs for algae, invertebrates, and fish in the range of 1.7-4 mg/L. 24 PAEs acquire unequivocal estrogenic activity under light irradiation that leads to the formation of 4-hydroxy PAEs. 27 A recent study reported that exposure to DEHP from hatching to adulthood accelerated the start of spawning and decreased the egg production of exposed marine madaka females whereas exposure to both DEHP and MEHP resulted in a reduction of the fertilization rate of oocytes spawned by untreated females paired with treated males. [START_REF] Ye | Exposure to DEHP and MEHP from hatching to adulthood causesreproductive dysfunction and endocrine disruption in marine medaka (Oryzias melastigma)[END_REF] DEHP induced histological changes in the testes and ovaries: the testes displayed a reduced number of spermatozoa, and the ovaries displayed an increased number of atretic follicles. The toxic effects of DEHP may be induced by both DEHP itself and DEHP metabolites, including MEHP. [START_REF] Ye | Exposure to DEHP and MEHP from hatching to adulthood causesreproductive dysfunction and endocrine disruption in marine medaka (Oryzias melastigma)[END_REF] Using a 72 h zebrafish embryo toxicity test, LC50 values of BBzP, DnBP and a mixture of six PAEs were 0.72, 0.63, and 0.50 mg/L, respectively. [START_REF] Chen | Toxicity and estrogenic endocrine disrupting activity of phthalates and their mixtures[END_REF] DEHP, DiDP, DiNP, and DnOP did not cause more than 50% exposed embryo mortality even at high concentrations. The symptoms caused by PAEs in aquatic organisms were death, tail curvature, necrosis, cardio edema, and no touch response. This work highlighted the developmental toxicity of BBzP and DnBP and the estrogenic endocrine disrupting activity of BBzP, DnBP, DEHP, and DiNP on intact organisms. [START_REF] Chen | Toxicity and estrogenic endocrine disrupting activity of phthalates and their mixtures[END_REF][START_REF] Oehlmann | A critical analysis of the biological impacts of plasticizers on wildlife[END_REF] The effects of PAEs on wildlife are multiples. The estrogenic effect is one of the important biological impacts of PAEs on wildlife. [START_REF] Harris | The estrogenic potential of phthalate esters in vitro[END_REF][START_REF] Oehlmann | A critical analysis of the biological impacts of plasticizers on wildlife[END_REF] They appear to act by interfering with the functioning of various hormone systems. [START_REF] Oehlmann | A critical analysis of the biological impacts of plasticizers on wildlife[END_REF] DMP, BBzP, DnBP, and DEHP have been shown to affect reproduction in annelids (both aquatic and terrestrial), molluscs, crustaceans, insects, fish and amphibians, to impair development in crustaceans and amphibians and to induce genetic aberrations. [START_REF] Oehlmann | A critical analysis of the biological impacts of plasticizers on wildlife[END_REF] Soil contaminated by PAEs also has a strong effect on the fauna and flora. [START_REF] Cartwright | Degradation and impact of phthalate plasticizers on soil microbial communities[END_REF] Some PAEs (DEHP, DnBP, BBzP) and their metabolites are estrogenic and exhibit adverse reproductive effects. [START_REF] Scholz | Ecotoxicity and biodegradation of phthalate monoesters[END_REF] For rodents, PAEs can effect on testicular atrophy, liver damage, decreased fertility, decreased fetal weight, increased kidney weights and antiandrogenic activity. The LC50 of DEHP is estimated at 40 g/kg and for DEP at 9.4 g/ kg. [START_REF] Benson | Hazard to the developing male reproductive system from cumulative exposure to phthalate esters-dibutyl phthalate, diisobutyl phthalate, butylbenzyl phthalate, diethylhexyl phthalate, dipentyl phthalate, and diisononyl phthalate[END_REF][START_REF] Aesn | Guide Pratique Des Substances Toxiques Dans les Eaux Douces et Littorales du Bassin Seine-Normandie[END_REF] The effect of DEHP and its metabolites is notably important in young animals and prenatal exposure during pregnancy. DEHP also affects the female fertility. Oral exposure to DEHP in rodents induced fetal death and malformations. DEHP is categorized as Group-2B agent by International Agency for Research on Cancer (IARC) and cinfirmed to have 2.4 times higher risk causing female breast cancer. 23 III.3. Regulations and Restrictions. Due to their potential health and environmental risks, PAEs have become a matter of worldwide concern. The WHO recommends the concentration of DEHP in drinking water below 8 μg/L. 86 U.S., Australia, Japan, and New Zealand have recommended a DEHP maximum value in drinking water to be 6 μg/L, 9, 100, and 10 μg/L respectively. [START_REF] Maycock | Review of England and Wales monitoring data for which a national or international standard has been set[END_REF] Serious questions have been raised about toy and childcare applications, especially if the toys are susceptible to being chewed or sucked by children. [START_REF] Marcilla | Study of the migration of PVC plasticizers[END_REF] The use of PAEs in toys or objects that can be placed in the mouth of children is now restricted or prohibited in many countries such as UE, U.S., Canada, Argentina, Brazil, and Japan. [START_REF]Chimical Inspection and Regulation Service (CIRS[END_REF][START_REF] Bette | California bans phthalates in toys for children[END_REF] Due to the possible endocrine disrupting effects of PAEs, environmental quality standards (EQSs) based on the annual average concentrations in aquatic environments have been calculated, [START_REF] Butwell | Endocrine Disrupting Chemicals in WastewaterA Review of Occurrence and Removal[END_REF] ranging from 20 μg/L for DEHP to 800 μg/L for DMP. However, EU proposed a guideline for environmental quality (NQE or Norme de qualitéenvironnementale) of 1.3 μg/L for DEHP in fresh and marine waters. [START_REF][END_REF] While Australian and New Zealand guidelines proposed trigger values of 5100, 1300, and 64.6 μg/L respectively for DMP, DEP, and BnBP as threshold values for the protections of 80% of species in freshwater (Table 2). However, for DEHP, there is insufficient data to derive a reliable trigger value neither in fresh and marine water (Table 2). The limit values established for DEHP in sludge for disposal onto farmland is proposed at 100 mg/kg dw, [START_REF]Working document on sludge 3rd draft Report[END_REF] while Danish Ministerial fixed the value at 50 mg/kg dw. 94 For natural sediment, Working Guidelines have been set for some PAEs (Table 2). The EU has included DnBP and DEHP in the list of substances suspected to cause endocrine disruption. [START_REF]Implementation of the Community Strategy for Endocrine DisruptersA Range of Substances Suspected of Interfering with the Hormone Systems of Humans and Wildlife[END_REF] DEHP has been classified by the EU as a substance causing toxic effects on fertility and development in humans. To minimize the health and environmental risk, DEHP has been replaced by DiNP and DiDP, which are Even if PAEs can be eliminated from different environmental matrices via various processes as reported in previous sections, their extensive use and permanent emissions have resulted in their ubiquitous presence in the environment. PAEs have been widely detected in air, surface water, sediments, and soil on a worldwide scale. Indoor air is also highly contaminated by PAEs released from plastics and consumer products in homes, in suspended particulate matter and house dust. [START_REF] Guo | Comparative assessment of human exposure to phthalate esters from house dust in China and the United States[END_REF]106 Concentration of PAEs in different environmental matrices has been reported in numerous papers and the compiled data are presented in Table 2S in Supporting Information.

The ubiquity of PAEs in the environment today has given rise to a heightened awareness of the biochemical and toxicological roles of these compounds in the biosphere. As reported previously, some PAEs have been added to the priority list and limited or recommended values have been set for the most abundant and toxic PAEs. The main objectives are the protection of ecological resources and human health. For a better representation of contamination level and ecotoxicological status of the environment, the composition of PAEs in different matrices and their contamination levels as listed in SI 2S. 2S).

Table 2S are presented in graph form and compared to the limits or recommended values.

IV.1. Fresh and Marine Surface Water. Numerous processes such as WWTP output, leaching, drainage, and atmospheric deposition are the major sources of PAEs in aquatic system. Among the large variety of PAEs, DMP, DEP, DiBP, DMEP, DnBP, BBP DEHP, and DnOP are among the most frequently detected in surface water (Supporting Information Table 2S). Figure 1 showed the composition of PAEs in fresh and marine water. Generally, studies focused on the six PAEs listed as priority substances which are the most toxic and also the predominant PAEs in the environment. Zheng et al. Marine and coastal environment present low level of PAEs compared to freshwater (Supporting Information Table 2S, Figure 1). For better evaluation the ecotoxicological state of aquatic system based on PAEs, the data were compared with the guidelines or recommend values. Figure 2 showed the 2S. 2S). contamination level of DEHP in fresh and marine water for worldwide scale compared to NQE valued fixed by EU. Based on NQE (1.3 μg/L) in fresh and marine water, majority of measured point exceeded the guideline value. The value is much higher than the eqs (0.17 μg/L) [START_REF] Marchand | Les contaminants chimiques dans le Directive Cadre sur l'Eau[END_REF] and ERLs (0.19 μg/ L) [START_REF] Van Wezel | Environmental risk limits for two phthalates, with special emphasis on endocrine disruptive properties[END_REF] (Figure 2). Some values were much higher than maximum allowance value of EQS reported by Butwell et al. [START_REF] Butwell | Endocrine Disrupting Chemicals in WastewaterA Review of Occurrence and Removal[END_REF] at 40 μg/L for DEHP. It is difficult to evaluate the effects of PAEs on the aquatic environment because several parameters should be taken into consideration. Some values have been proposed by many research groups as reported previously. Predected effect concentration (PEC) which identifies the concentration above which harmful effects on organisms were expected to occur frequently has been proposed at 3.2 μg/L. [START_REF] Naito | Screening-level risk assessment of di(2-ethylhexyl)phthalate for aquatic organisms using monitoring data in Japan[END_REF] Above all, it is clear that the majority of concentrations shown in Figure 2 are considerably higher than all the limit values (PEC, NQE, ERLs) previously reported.

The contamination levels of DnBP, DMP, DEP and BBzP in fresh and marine water is presented in Supporting Information Figures 2S to 4S. For DnBP, notably few samples are present at the level below the lowest observed effect concentration (LOEC) and ERLs values set at 2 and 10 μg/L, respectively. In some cases, the concentrations were higher than the PGW value fixed at 100 μg/L (Supporting Information Figure 2S). Thus, DnBP may affect not only aquatic organisms but also the groundwater resources. DMP and DEP were present under the EQS level except for the concentration reported by Fatoki and Ogunfowoka 108 from Nigeria (Supporting Information Table 2S; Figure 3S). Their concentrations were reported at very high levels, sometimes exceeding 500 mg/L. The EQS of BBzP has been set at 20 μg/L, with the maximum value set at 100 μg/L. [START_REF] Butwell | Endocrine Disrupting Chemicals in WastewaterA Review of Occurrence and Removal[END_REF] Based on these EQS values, fresh and marine water possess acceptable levels for this compound. Only one value detected at Al-Khobar, Saudi Arabia was present at a high level (36.48 μg/ L) and exceeded the EQS.

IV.2. Drinking Water. PAEs present in drinking water can generally reach several μg/L, and in some cases, their levels can reach on the order of mg/L. 108 Figure 3 presents worldwide distribution of each PAE currently detected in drinking water. There is no predominant PAE notable among the large variety of PAEs detected in drinking water (i.e., mineral water, tap water, fountain water). Actually, it is difficult to determine the 2S). 2S). Figure 4 presents the contamination levels of drinking water by DEHP compared to the drinking water standards. The concentrations of DEHP most often detected in drinking water were in the range of a few hundred ng/L. Compared to the drinking water standard, the DEHP concentration does not exceed the guideline value, with the exception of mineral water (Mattoni) commercialized in the Czech Republic, where the concentration exceeded 9 μg/L. 109 Moreover, PAEs in drinking water can be removed by some novel technology such as the simultaneous electrocoagulation and electrofiltration process). [START_REF] Yang | Monitoring and removal of residual phthalate esters and pharmaceuticals in the drinking water of Kaohsiung City, Taiwan[END_REF] This process coupled with the tubular carbon nanofiber/carbon/alumina com-posite membrane has been used to PAEs in drinking water with satisfactory revoval yield. The remove efficiencies ranged from 42 to 78%. [START_REF] Yang | Monitoring and removal of residual phthalate esters and pharmaceuticals in the drinking water of Kaohsiung City, Taiwan[END_REF] IV.3. Sediment. In sediments, DnBP and DEHP were found in abundance (Supporting Information Table 2S; Figure 5). We note that DnBP can be used as a predictive indicator for the sediment ∑ 16 PAEs concentration. 110 DEHP concentrations have been compared to the ERLs, NOEC and PEC values. All measured levels are below the ERLs, NOEC, MAEC, and PEC values with the exception of the data reported for Lakes water from Beijing and Taiwan (Figure 6).

Environmental Science & Technology

IV.4. Sludge. Presently, six PAEs were detected in wastewater, sewage sludge and compost samples. Their sum can exceed 250 mg/kg (Supporting Information Table 2S; Figure 7). In general, DEP, DnBP, and DEHP were the predominant PAEs in sludge and compost. However, composting can reduce the concentrations of PAEs initially present in sewage sludge, 111,112 with removal rates of up to 77.3-100%. 112,113 Figure 7 shows the composition of PAEs in various types of sludge. In sludge, the removal rates of PAEs with short alkyl chains length were higher than those with long alkyl chains length. [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF]114 PAEs with short alkyl chains are more easily biodegraded and mineralized than those with long alkyl chains, of which some are considered resistant to degradation. However, during the composting, long alkyl chain length compounds could be transformed to compounds with shorter alkyl chain length compounds. [START_REF] Cartwright | Degradation and impact of phthalate plasticizers on soil microbial communities[END_REF]114 Amir et al. 114 has previously reported the transformation mechanism for the conversion of long alkyl chain length to DnBP, DEP, and DMP. 2S). 2S).

The half-lives of DEHP were calculated at 45.4 days for lagooning sludge and 28.9 days for activated sludge. 114 The degradation rates of the four PAEs were DBP > BBzP > DEP > DEHP. 125 Generally, PAEs can be eliminated by WWTP with satisfactory removal yields from wastewater. [START_REF] Dargnat | Phthalate removal throughout wastewater treatment plant: case study of Marne Aval station (France)[END_REF][115][116][117][118] However, PAEs can accumulate in sludge which can be recycled for application on agricultural soil, which could then be a source of soil and water pollution by leaching or draining. Moreover, during a heavy rain period, WWTP can be overflown, thus leading to the contamination of the surrounding environment. Figure 8 shows the worldwide contamination levels of DEHP in sludge.

Most of different types of sludge contain high levels of DEHP that can exceed the limit value set by the EU and Danish Ministerial for land application (Figure 8). However, it is noteworthy that composting can be an effective approach to remove PAEs from sludge before land application because it reduces the PAEs initially present in sludge. 111,112 Given the high half-life of PAEs in soil, stricter controls should be adopted before using sludge as a soil amendment. As reported in a previous section, the half-life of DEHP was estimated to be anywhere from 30 days 47 to a few hundred days. [START_REF] Cartwright | Degradation and impact of phthalate plasticizers on soil microbial communities[END_REF] IV.5. Soil. Atmospheric deposition and sewage sludge used as a soil amendment are the major sources of PAEs in soil. Vikelsøe et al. 118 have demonstrated the correlation between PAEs concentration in soils and the level of sludge amended. In soil, DnBP and DEHP were the most abundant PAEs (Figure 9). DnOP and DiBP were also frequently detected, but their concentrations were much lower than the concentrations of DnBP and DEHP. Generally, noncultivated soils contain the lowest contents of PAEs, suggesting that these types of pollutants are largely derived from human agricultural activities. To better evaluate the ecological risk, DEHP concentrations have been compared to Protection of Ecological Resources (PER) and PGW values (Figure 10). The concentration of DEHP is below the PGW level. In general, the DEHP concentrations in soil were below the levels of PER, with the exception of the urban soil measured at Guanghou in China (Figure 10). However, the DEHP concentrations often exceed the ERL values (1 mg/kg wt). 2S). 2S).

The contamination levels of DMP, DEP, DnBP, and DnOP are presented in Supporting Information Figures 5S and6S. The DMP and DEP contamination levels were very low and did not exceed 0.4 mg/kg dw. Moreover, their values were much lower than the PGW and PER values set by the New York State Department of Environmental Conservation in 2010. The DnOP contamination was also detected at lower levels than the PER value set at 0.91 mg/kg dw. However, in a few cases DnBP was detected at levels higher than the PER and PGW values (Figure 12).

IV.6. Indoor and Outdoor Air. DnBP and DEHP were detected as the predominant PAEs in air. [START_REF] Wang | Indoor phthalate concentration and exposure in residential and office buildings in Xi'an, China[END_REF][START_REF] Peijnenburg | Occurrence of phthalate esters in the environment of the Netherlands[END_REF][START_REF] Teil | Atmospheric fate of phthalate esters in an urban area (Paris-France)[END_REF]119,120 The total atmospheric levels of ∑ 6 PAEs (DMP, DEP, DnBP, BBzP, DEHP, and DnOP) was 57.4 ng/m 3 in Paris. [START_REF] Teil | Atmospheric fate of phthalate esters in an urban area (Paris-France)[END_REF] As PAEs are released from anthropogenic activities, their concentrations are present at higher levels in a urban center than in suburban areas. ∑ 6 PAEs were detected at 97 ng/m 3 in the urban center versus 27.8 ng/m 3 in the suburban areas. 119 In the remote Arctic, the total concentration of atmospheric PAEs (i.e., ∑ 6 PAEs) was detected at 2.14 ng/m 3 . [START_REF] Xie | Occurrence and air-sea exchange of phthalates in the Arctic[END_REF] Worldwide, ∑ 6 PAEs were detected at higher levels in indoor air than outdoor air: 1014-1828 ng/m 3 in China, [START_REF] Guo | Comparative assessment of human exposure to phthalate esters from house dust in China and the United States[END_REF][START_REF] Zhang | Phthalate esters (PAEs) in indoor PM 10 /PM 2.5 and human exposure to PAEs via inhalation of indoor air in Tianjin, China[END_REF] 1289-2386 ng/m 3 in Sweden, 106 545-2160 ng/m 3 in the U.S. 121,122 DMP, DEP, DiBP, DnBP, and DEHP were detected in marine aerosols. Their total concentrations were 0.79-12.4 ng/ m 3 , with an average of 2.6 ng/m 3 , which were higher than those reported in the North Sea to the high Arctic atmosphere (0.38-1.02 ng/m 3 ) during the summer of 2004. [START_REF] Xie | Atmospheric concentrations and air-sea exchanges of phthalates in the North Sea (German Bight)[END_REF] A possible source of PAEs in the Arctic troposphere may be associated with long-range transport from midlatitudes and the subsequent deposition on the snow/ice sheet. The deposited PAEs onto snow and ice can also be released into the atmosphere with the increase of the ambient temperature during the spring and summer months. 123 PAEs have been suggested to contribute to secondary oxidation products in organic aerosol fractions. 124,125 Phthalic acid dominated the isomeric composition, which is consistent with those reported in continental aerosols. 119 We note that a limiting value for this compound in ambient air has not been established.

Figures 11 and12 show the composition of PAEs in air in both the gas phase and dust phase. In the gas phase, DiBP and DnBP were present in the highest frequency, which led to these compounds possessing the highest concentrations of the PAEs investigated. DEHP was also frequently detected in the gas phase air, but its concentration was much lower than the concentrations detected for DiBP and DnBP (Figure 11). In the dust phase, DEHP was the predominant PAE identified, followed by DnBP and DiBP (Figure 12). IV.7. PAEs in Wildlife. PAEs are hydrophobic compounds with logK OW can be up to 12.06 (Table 1) which indicate that they have strong ability to accumulate into organisms. Hydrophobicity of PAEs increase with increase of carbon leng chain. The contamination levels of some PAEs in biota including fishes, mammals, algae and others species are listed in Table 3S in SI. Fishe species were reported to accumulate large variety of PAEs both parent and metabolite products including MPEs. PAEs and their metabolites were detected from the top of food chain (plankton, algae) to predator organisms (fish, marine mammals). [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF][126][127][128][129][130][131] Plankton and shellfish can accumulate individual PAE from not detected (nd) level to few hundreds ng/g. 130,131 For freshwater ecosystem, the concentrations of individual PAE detected in fish species were in the range of nd to few hundreds μg/g. 127,128 Two order of magnetude lower were reported for marine fish 127,129 (detailed values are given in Supporting Information Table 3S). In marine mammal, individual PAE was detected in the range of <LOQ to few μg/g. 130,131 The highest was detected in liver of Beluga whale Delphinapterus leucas which the 2S). 2S).

Environmental Science & Technology

Critical Review DOI: 10.1021/es505233b Environ. Sci. Technol. XXXX, XXX, XXX-XXX L concentration can be up to 4.15 μg/g of DEHP in wet weight animal. 130 Bioaccumulation/Bioconcentration factors (BAF or BCF) have been calculated for PAEs. A BCF or BAF >1000 indicates a high capacity for the species to accumulate or concentrate the pollutant. 132 BAF and BCF of individual PAEs in wildlife are compiled in Supporting Information Table 5S. Few study was focused on BAF of PAEs in wilelife. The BAF of individual PAE (DEP, DnBP, BBzP, DEHP, and DnOP) in three mammals and five invertebrates <0.25 exepted for DnOP in inverterbrates that can be up to 2400 (Supporting Information Table 5S). 133 Fishs have been reported to concentrate PAEs at significant level with total BCF of 57, 117, 45-663, 11-900, 207, and 2668-2125 mL/g/wet respectively for DMP, DEP, BBzP, DEHP, DiOP, and DnDP. Staples et al. [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF] have compiled litherature data on the total BCF for aquatic organisms. They reported that crustacea and insect can accumulate DnBP with total BCF of 185-1485 and 458-714 mL/g/wet, respectively. Total BCF of 100 mL/g/wet has been reported for BBzP for Mollusca. [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF] Total BCF of DHxP has been reported to be 999-5269 mL/g/wet for crustacea. DnOP can bioconcentrate various aquatic species including in algae, mollusca, crustacean and insecta with total BCF of 8412, 699, 1429, and 1338 mL/ g/wet, respectively. [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF] Similarly, DEHP were measured at high level of total BCF at 987, 264-2627, 83-3916, and 315-1892 mL/g/wet respectively for algae, mollusca, crustacean and insect. [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF] Total BCF of DiNP in mollusca was reported at 1844 mL/g/wet. Total BCF of DiDP were measured at 2998-3977 and 90-147 mL/g/wet for mollusca and crustacean. [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF] DnBP, DnOP, and DEHP were the three PAEs that can be bioconcentrated at high level in fish, shellfish and green algae (Supporting Information Table 5S). Low molecular weigh PAEs (DMP and DEP) were detected to accumiulate at low level in aquatic species. The low values of BAF and BCF for some PAEs may be due to the fact that PAEs can be degraded or metabolized be species. Indedd, microbes from diverse habitats have been showed to degrade PAEs. [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF] High metabolite product of DEHP (MEHP) has been detected in plankton 130 which indicate that plankton can biodegrade DEHP by converting to MEHP. Thus, BCF can be an important factor of PAEs fate in the environment because it leads to biodegradation. Primary biodegradation half-lives of PAEs range from <1 day to ∼2 weeks and clear trends between differents PAEs or between fresh water and marine waters are not apparent. [START_REF] Staples | The environmental fate of phthalates esters: A literature review[END_REF] Ultimate degradation half-lives of DEHP (averaged about 12-67 days depend on temperature) are about an order of magnitude higher compared to primary biodegradation half-lives.

■ CONCLUSIONS

PAEs can be degraded by different biotic and abiotic pathways, as such they are not expected to be highly persistent in aquatic and terrestrial environments (air, water, sediment, and soil). Global half-lives of PAEs in air vary from few hours to few days. PAEs in water can be eliminated by hydrolysis, photolysis, photooxidation, and biodegradation. However, there is a paucity of data dealing with accurate description of degradation processes for the complete set of PAEs. Current knowledge shows that degradation half-lives of individual PAE ranges from a few days to months in soils and sediments according to the environmental conditions. Biodegradation activity appears to be greater than abiotic degradation in surface waters, sediments and soils. PAEs with low molecular weight are more easily biodegraded than those with higher molecular weights. In natural environments, large variations of degradation of PAEs are caused by their physicochemical properties, the type of bacterial strains, temperature variations and nutritional conditions. Primary degradation half-life in water is expected to be on the order of less than 1 week, whereas the half-lives in soils can be up to several months. Longer half-lives are more likely under anaerobic conditions and in cold, nutrient poor environments.

PAEs can be eliminated from different environmental matrices via various processes. However, their extensive use and permanent emissions have resulted in their ubiquitous presence in the environment. These products can cause toxic effects on fertility and the development of humans as well as on many aquatic and terrestrial species. Consequently, the chronic exposure of PAEs to aquatic organisms and humans raises many questions. This study contributes in establishing the biogeochemical cycle of PAEs in the environment according to anthropogenic, hydrological and climatic factors.

■ ASSOCIATED CONTENT

* S Supporting Information Additional information as noted in the text. This material is available free of charge via the Internet at http://pubs.acs.org.

■ AUTHOR INFORMATION

Corresponding Author *Phone: +33(0)3-28-77-85-24; fax: +33(0)3-20-43-48-22; email: sopheak.net@univ-lille1.fr.

Notes

The authors declare no competing financial interest.

Figure 1 .

 1 Figure 1. Composition of PAEs in different types of fresh and marine water for worldwide scale; detail values and references are given on Supporting Information Table2S.

Figure 2 .

 2 Figure 2. Worldwide contamination levels of DEHP in fresh and marine water compared to the NQE and EQS values (Detailed values and references are given in Supporting Information Table2S).

  107

  measured the concentration of 15 PAEs in water both in dissolved phase and associated with SSM. The ∑ 6 PAEs represents 64.8 and 66.9% of the ∑ 15 PAEs respectively in dissolved phase and associated with SSM. DEHP and DnBP were predominant PAEs following by DiBP and BBzP. 107 Figure 1 confirms the predominant of DnBP and DEHP in fresh and marine water.

Figure 3 .

 3 Figure 3. Composition of PAEs drinking water for worldwide scale; detailed values and references are given on Supporting Information Table2S.

Figure 4 .

 4 Figure 4. Worldwide contamination levels of DEHP in drinking water compared to the drinking water standard (Detailed values and references are given in Supporting Information Table2S).

Figure 5 .

 5 Figure 5. Worldwide composition of PAEs in sediment (Detailed values are given in Supporting Information Table2S).

Figure 6 .

 6 Figure 6. Contamination levels of DEHP in sediment compared to the NOEC, MAEC, ERLs, PEC and values (Detailed values and references are given on Supporting Informaiton Table2S).

  .1021/es505233b Environ. Sci. Technol. XXXX, XXX, XXX-XXX I predominant PAE because targeted compounds change from one study to another. Based in Figure 3, DMP, DEP, DnBP, and DEHP were the PAEs most often detected in drinking water. Nevertheless, even if six PAEs were added onto the priority list of the U.S. EPA, the drinking water standard for DEHP has been the only one established.

Figure 7 .

 7 Figure 7. Composition of PAEs in sludge (Detailed values and references are given in Supporting Information Table2S).

Figure 8 .

 8 Figure 8. Worldwide contamination levels of DEHP in sludge compared to the limiting value (Detailed values and references are given in Supporting Information Table2S).

21

 21

Figure 9 .

 9 Figure 9. Worldwide composition of PAEs in soil (Detailed values and references are given in Supporting Information Table2S).

Figure 10 .

 10 Figure 10. Worldwide contamination levels of DEHP in soil compared to the limiting values for PER and PGW (Detailed values and references are given in Supporting Information Table2S).

Figure 11 .

 11 Figure 11. Worldwide contamination levels of PAEs in air (gas phase) (detailed values and references are given in Supporting Information Table2S).

Figure 12 .

 12 Figure 12. Worldwide contamination levels of PAEs in air (dust phase) (detailed values and references are given in Supporting Information Table2S).

Table 2 .

 2 Regulations and Guidelines Applicable to Some PAEs Are Listed in Priority List a

				soil (mg/kg dw)
		DMP	DEP	DnBP	BBzP		DEHP	DnOP
	ERLs (fresh wt) 21			0.7				1
	PER 95	200	100	0.014			239	0.91
	PGW 95	27	7.1	8.1		122		435
				water (μg/L)
				DEP	DMP	DEHP	BBzP	DiBP	DnBP
	drinking water standard					8, 86 6 96
	PEC					3.2 97
	EQS					0.17 98
	EQS (Max.) 91			200	800	20	20	8 (DiBP+ DnBP)
				(1000)	(4000)	(40)	(100)	(40)
	trigger values for freshwater (level of protection of species in %)*	3000 (99%)	900 (99%)	ID		9.9 (99%)
				3700 (95%)	1000 (95%)			26 (95%)
				4300 (90%)	1100 (90%)			40.2 (90%)
				5100 (80%)	1300 (80%)			64.6 (80%)
	Trigger values for marine water *		ID	ID	ID		ID
	NQE for fresh, marine water					1.3 92
	ERLs				0.19 21			10 21,99
	PGW							100 100
	NOEC					77 97		22.8 101
								500 102
				sediment (mg/kg dw)
		DMP	DEP	BBzP	DnBP	DnOP	DEHP	DiNP
	ERLs 21				1.82			1
	PNEC				3.1 90
	PEC							33.7 103	17.8 104
	NOEC	0.53 105		0.049 104	2.2 105	0.58 105	0.47 105
	MAEC (marine)		0.61 105	0.64 104	17 105	45 105		0.78 105
				sludge (mg/kg dw)
	land application						100 for DEHP 93

considered not hazardous. Six PAEs (DMP, DEP, DnBP, BBzP, DEHP, and DnOP) have been included in the list of priority pollutants compiled by both the U.S. EPA and the EU and on the list of priority pollutants in Chinese waters.

14

Table 2 presents different limited or recommended values available in different environmental matrices. IV. Occurrence and Ecotoxicological State of PAEs.

■ ACKNOWLEDGMENTS

We are grateful for the financial support provided by the MERMEX/MISTRALS project and Labex OT-Med. We thank the associate editor and the anonymous reviewers for improving the quality of the manuscript. We acknowledge the financial support from the PACA region, which provided a PhD scholarship for A. Paluselli.