Novel decomposition of polycarbonate and effect for marine ecosystem.

Analysis of pollution of the ocean plastics is presently being extensively carried out but special attention should be direct to matters. It is widely believed that plastic dose not decompose in the ocean. Certain contaminants, bisphenol-A (BPA) that serves the material for polycarbonate (PC) and epoxy resin (EPX) both of which may possibly be elute or degrade from commercial products, have often been detected in rivers, lakes and oceans. To clarify in detail the extend of this impact of this situation, purified PC (BPA free) was decomposed at temperatures range 50-230 °C. PC was seen to start decomposing at 50 °C over a 3 day period to generated 11 µg kg-1 BPA. Based on the rate constants of BPA, the activation energy was calculated 42.0 kJ mol-1. Since this value is almost same as the EPX and polystyrene (PS) of each decomposition. Based on the PC decomposition rate and the actual BPA value in the deep sea, the 280 million metric tons (MT) BPA in the world ocean was estimated. Unlike plastics, BPA shows endocrine disrupting in fish. It should thus be considered that degraded PC and EPX pose a serious threat to the marine ecosystem, directly.

Aquatic toxicity and fate of styrene oligomers in the environment.

Styrene oligomers (SOs) are ubiquitous contaminants that appear in the environment, sometimes to significant extent (see section 3.1). Despite the ongoing international debate on the human health risks posed by SOs, to the best of my knowledge, there are no studies on the aquatic toxicity and environmental fates (biodegradation and atmospheric degradation) of SOs in the environment. This study is to predict the aquatic toxicity and environmental fate of SOs by using the US EPA EPI suite program as an in-silico method. For better understanding, the risks and fates of SOs are compared with those of the well-known bisphenol A (BPA) and styrene monomer (SM or styrene). As a result of this study, SOs are predicted to be relatively more toxic than BPA and SM to aquatic and terrestrial organisms in the freshwater, marine, and terrestrial environments. In particular, the biodegradability of SOs is predicted to be relatively very slow in the environment, and most SOs are more likely to be effectively decomposed by hydroxyl radicals than by ozone in the atmosphere. As a result, this study can contribute to motivating understanding of the aquatic toxicity and fate of ubiquitous SOs in the environment.

Sandy beaches as hotspots of bisphenol A.

Bisphenol A (BPA) poses a serious environmental threat and health concern. This study presents the global monitoring of BPA on oceanic sandy beaches. According to monitoring results, many beach sands contain a harmful concentrations of BPA. Likewise, styrene oligomers (SOs), anthropogenic chemicals derived from polystyrene plastics, show similar concentrations as BPA. This study shows a strong, positive correlation between BPA and SOs. The results indicate that probably BPA-containing materials including micro- and nano-plastics can be an important source of BPA to the sand beaches. Therefore, BPA presents potential health risks to people spending considerable time on the beach.

Physicochemical properties of styrene oligomers in the environment.

Currently, styrene oligomers (SOs) are persistent contaminants that are present in the environment globally. SOs are artificial substances originating from styrene-based polymer materials, mainly including PS plastic, resin, and rubber. However, the behavior of SOs in the environment is not well-understood yet due to the scarcity of experimental data. The objective of this study was to use in-silico tool to estimate key physicochemical properties of these SOs. The US EPA EPI suite program was used to predict SOs' physicochemical properties including solubility, vapor pressure, LogKow, Henry's constant, LogKoc, and fugacity-based multimedia mass balance. Although styrene monomer (SM) and SOs have structural similarity, the physicochemical properties of SOs are significantly different from those of SM, a precursor of SOs. In particular, it is estimated that as much as the heavy molecular weight, most SOs persist for comparable periods of time in a sandy environment. Although there is uncertainty, this preliminary in-silico study provides a sufficient reason to assure an experimental study to better determine properties of SOs.

Evidence of transport of styrene oligomers originated from polystyrene plastic to oceans by runoff.

This study demonstrates for the first time that styrene oligomers (SOs), which are indicators of polystyrene (PS) plastic contamination in the environment, are transported from land to the ocean. Samples of sand and seawater were taken from the coastline of the Tokyo Bay over the past four years, and all samples of both sand and seawater were found to contain SOs such as styrene monomer (SM), styrene dimers (SD), and styrene trimers (ST), with the concentration distributions of these being in the order of ST > SD > SM. The concentrations of these SOs are linearly proportional to monthly precipitation. These results indicate that various land-based SOs sources are connected with the estuary, a substantial amount of which are transported into Tokyo Bay through runoff as overland flow. As a result, runoff by precipitation is a potential transport pathway of land-based SOs sources. This finding is of interest in terms of both the extent of PS plastic pollution and the transport of SOs to the ocean. CAPSULE ABSTRACT: The assessment of the transport of styrene oligomers (SOs) in the coastal environment is performed.

Qualitative assessment to determine internal and external factors influencing the origin of styrene oligomers pollution by polystyrene plastic in coastal marine environments.

The objective of this study is to investigate the qualitative contribution of internal and external factors of the area contaminated by polystyrene (PS) in coastal marine environments. This study is based on the extensive results of monitoring the styrene oligomers (SOs) present in sand and seawater samples along various coastlines of the Pacific Ocean. Here, anthropogenic SOs is derived from PS during manufacture and use, and can provide clues about the origin of SOs by PS pollution. The monitoring results showed that, if the concentration of SOs in water is higher than those concentrations in beach sand, this area could be affected by PS plastic caused by an external factor. On the other hand, if the concentration of SOs is higher in the beach sand, the region can be mainly influenced by PS plastic derived from its own area. Unlike the case of an external factor, in this case (internal influence), it is possible to take policy measures of the area itself for the PS plastic problem. Thus, this study is motivated by the need of policy measures to establish a specific alternative to the problems of PS plastic pollution in ocean environments.

Monitoring of styrene oligomers as indicators of polystyrene plastic pollution in the North-West Pacific Ocean.

Styrene oligomers (SOs) as global contaminants are an environmental concern. However, little is known on the distribution of SOs in the ocean. Here, we show the distribution of anthropogenic SOs generated from discarded polystyrene (PS) plastic monitored from the coastal ocean surface waters (horizontal distribution) and deep seawaters (vertical distribution) in the North-West Pacific Ocean. SOs concentrations in surface seawater and deep seawater ranged from 0.17 to 4.26 µg L-1 (total mean: 1.48 ± 1.23 µg L-1) and from 0.31 to 4.31 µg L-1 (total mean: 1.32 ± 0.87 µg L-1), respectively. Since there is no significant difference in the mean concentrations, SOs seems to be spread across marine environment selected in this study. Nevertheless, regional SOs appears to persist to varying degrees with their broad horizontal and vertical distribution in the ocean. Each horizontal and vertical distribution of SOs differs by approximately 1.95-2.57 times, probably depending on the events of weather and global ocean circulation. These results provide the distribution pattern of SOs for assessing environmental pollution arising from PS plastic.

Global styrene oligomers monitoring as new chemical contamination from polystyrene plastic marine pollution.

Polystyrene (PS) plastic marine pollution is an environmental concern. However, a reliable and objective assessment of the scope of this problem, which can lead to persistent organic contaminants, has yet to be performed. Here, we show that anthropogenic styrene oligomers (SOs), a possible indicator of PS pollution in the ocean, are found globally at concentrations that are higher than those expected based on the stability of PS. SOs appear to persist to varying degrees in the seawater and sand samples collected from beaches around the world. The most persistent forms are styrene monomer, styrene dimer, and styrene trimer. Sand samples from beaches, which are commonly recreation sites, are particularly polluted with these high SOs concentrations. This finding is of interest from both scientific and public perspectives because SOs may pose potential long-term risks to the environment in combination with other endocrine disrupting chemicals. From SOs monitoring results, this study proposes a flow diagram for SOs leaching from PS cycle. Using this flow diagram, we conclude that SOs are global contaminants in sandy beaches around the world due to their broad spatial distribution.

Biodegradation of perfluorooctanesulfonate (PFOS) as an emerging contaminant.

Perfluorooctanesulfonate (PFOS) is a compound of global concern because of its persistence and bioaccumulation in the environment. Nevertheless, little is known of the potential for PFOS biodegradation, even though the importance of characterizing the function and activity of microbial populations detected in the environment has been discussed. This study focused on the biodegradation of PFOS by a specific microorganism. Through this study, we have identified the aerobic microorganism for the specific decomposition of PFOS from wastewater treatment sludge, as a well-known sink for environmental PFOS. This species was Pseudomonas aeruginosa strain HJ4 with a 99% similarity, a mesophilic rod type bacteria (30-37°C). A pH range of 7-9 was determined to be optimal for the growth of strain HJ4. In this study approximately 67% over a range of concentrations (1400-1800µgL(-)(1)) for PFOS was biologically decomposed by P. aeruginosa after 48h incubation. This result is reported here for the first time, which strongly pertains to the efficient biodegradation of PFOS. Therefore, our study is considered a major advancement in sustainable PFOS treatment.

Regional distribution of styrene analogues generated from polystyrene degradation along the coastlines of the North-East Pacific Ocean and Hawaii.

Beach sand and seawater taken from the coastlines of the North-East Pacific Ocean and Hawaii State were investigated to determine the causes of global chemical contamination from polystyrene (PS). All samples were found to contain styrene monomer (SM), styrene dimers (SD), and styrene trimers (ST) with a concentration distribution of styrene analogues in the order of ST > SD > SM. The contamination by styrene analogues along the West Coast proved more severe than in Alaska and other regions. The Western Coastlines of the USA seem be affected by both land- and ocean-based pollution sources, which might result from it being a heavily populated area as the data suggest a possible proportional relationship between PS pollution and population. Our results suggest the presence of new global chemical contaminants derived from PS in the ocean, and along coasts.

New analytical method for the determination of styrene oligomers formed from polystyrene decomposition and its application at the coastlines of the North-West Pacific ocean.

The pollution caused by plastic debris is an environmental problem with increasing concern in the oceans. Among the plastic polymers, polystyrene (PS) is one of the most problematic plastics due to the direct public health risk associated with their dispersion, as well as the numerous adverse environmental impacts which arise both directly from the plastics and from their degradation products. Little is known about their potential distribution characteristics throughout the oceans. For the first time, we report here on the regional distribution of styrene monomer (SM), styrene dimers (SD; 2,4-diphenyl-1-butene, SD1; 1,3-diphenyl propane, SD2), and styrene trimer (2,4,6-triphenyl-1-hexene: ST1), as products of PS decomposition determined from samples of sand and seawater from the shorelines of the North-West Pacific ocean. In order to quantitatively determine SM, SD (=SD1+SD2), and ST1, a new analytical method was developed. The detection limit was 3.3 µg L(-1), based on a signal-to-noise ratio of three, which was well-suited to quantify levels of SM, SD, and ST1 in samples. Surprisingly, the concentrations of SM, SD, and ST1 in sand samples from the shorelines were consistently greater than those in seawater samples from the same location. The results of this study suggest that SM, SD, and ST1 can be widely dispersed throughout the North-West Pacific oceans.

The formation of reactive species having hydroxyl radical-like reactivity from UV photolysis of N-nitrosodimethylamine (NDMA): kinetics and mechanism.

This study focuses on the detailed mechanism by which N-nitrosodimethylamine (NDMA) is photolyzed to form oxidized products, i.e., NO(2)(-) and NO(3)(-), and reveals a key reactive species produced during the photolysis of NDMA. Under acidic conditions, NO(2)(-) formed from the photodecomposition of NDMA was more prevalent than NO(3)(-). In this result, key species for the formation of NO(2)(-) are presumably N(2)O(3) and N(2)O(4) as termination products as well as NO and O(2) as reactants. Conversely, under alkaline conditions, NO(3)(-) was more prevalent than NO(2)(-). For this result, a key species for NO(3)(-) formation is presumably peroxynitrite (ONOO(-)). A detailed mechanistic study was performed with a competition reaction (or kinetics) between NDMA and p-nitrosodimethylaniline (PNDA) probe for hydroxyl radical (OH). It is fortuitous that the second-order rate constant for NDMA with an unknown reactive species (URS) was 5.13×10(8) M(-1) s(-1), which was similar to its published value for the reaction of NDMA+OH. Our study results showed that a key reactive species generated during NDMA photo-decomposition had hydroxyl radical-like reactivity and in particular, under alkaline conditions, it is most likely ONOO(-) as a source of nitrate ion. Therefore, for the first time, we experimentally report that an URS having OH-like reactivity can be formed during photochemical NDMA decomposition. This URS could contribute to the formations of NO(2)(-) and NO(3)(-).

Pentachlorophenol decomposition by electron beam process enhanced in the presence of Fe(III)-EDTA.

This study focuses on the enhanced decomposition of pentachlorophenol (PCP) in an electron beam (E-beam) process. To attain this objective, we investigated a synergistic effect of ferric-ethylenediamineacetate (Fe(III)-EDTA) and H(2)O(2) as additives to produce additional hydroxyl radical (*OH) at low dose. In this process, aqueous electron and hydrogen atom rapidly react with O(2) molecules, thereby forming hydroperoxyl/superoxide anion radical (HO2*/O(2)(-)), which reduces the Fe(III)-EDTA into Fe(II)-EDTA. Further *OH is produced by a well-known Fenton-like reaction of Fe(II)-EDTA with H(2)O(2) formed newly in E-beam. The complete decomposition of the initial PCP at 0.1mM was enhanced even at very low dose (<10 kGy) with 20 microM Fe(III)-EDTA and H(2)O(2) less than 1mM. This observation was supported by the increased amount of Cl(-) produced by the decomposition of PCP. Thus, in the presence of Fe(III)-EDTA during E-beam irradiation, the HO2*/O(2)(-)-driven Fenton-like reaction produces much more ()OH, which is significant for the complete degradation of PCP.

A kinetic method for HO2*/O2*- determination in advanced oxidation processes.

A new kinetic method is developed for the determination of hydroperoxyl radical (HO(2)(*))/superoxide radical (O(2)(*)(-)) in aqueous solution, and the calibration using a kinetic half-life technique is also established for determining the concentration of HO(2)(*)/O(2)(*)(-) as produced in the UV/H(2)O(2) process. This new method is based on the reduction of Fe(3+)-EDTA into Fe(2+)-EDTA by HO(2)(*)/O(2)(*)(-) and the well-known Fenton-like reaction of H(2)O(2) and Fe(2+)-EDTA to yield the hydroxyl radicals (OH(*)). Benzoic acid scavenges the OH radicals to produce hydroxybenzoic acids, which are analyzed by fluorescence detection (lambda(ex) = 320 nm; lambda(em) = 400 nm). The limit of detection for the new method depends on the pH values, and it is determined as 3.22 x 10(-)(11) M with signal-to-noise ratio of 2 at pH 5. In addition, the present technique has the advantage of using inexpensive and easily available nonenzymatic reagents that do not require the specific instrument and chemicals and of being insensitive to the moderate concentration of possible interferences often found in aqueous phase.