Source- and polymer-specific size distributions of fine microplastics in surface water in an urban river.

There is increasing concern about the environmental behaviors of microplastics (MPs), in particular fine MPs (FMPs), such as their concentrations, sources, size distributions, and fragmentation by weathering in waters. However, there is little information about size distributions of MP polymer types and their relationships to their sources. Here, we analyzed concentrations, compositions, and size distributions of 18 polymer types of MPs of >20 µm by micro-Fourier transform infrared spectroscopy with a novel pretreatment method in surface waters at five sites from the headwaters to the mouth of a Japanese river, and in influent and effluent from a sewage treatment plant (STP). The microplastic concentrations ranged from 300 to 1240 particles/m3 in surface waters. Cluster analysis identified two primary sources of MPs: residential wastewater at the headwater site and non-point sources from urban areas at downstream sites; concentrations of chemical contaminants from STPs were much higher at the downstream sites. The median particle sizes (D50) of MPs increased in urban areas at the downstream sites and were larger than those in influent and effluent. These results imply the release of larger MPs from non-point sources in urban areas. The size distributions of each polymer and all MPs could be fitted significantly to the Weibull distribution function. Values of D50, shape parameters, and scale parameters estimated from the functions were useful indicators for evaluating size distributions in detail. A significant positive correlation of D50 with the tensile strengths of virgin polymers among 13 dominant polymers detected in the surface water suggests that the fragmentation properties of each polymer are influenced by its physical strength. Multidimensional analysis with concentrations, polymeric compositions, and size distributions of MPs, including FMPs, could provide useful information about their sources and their environmental behaviors.

Neonicotinoids disrupt aquatic food webs and decrease fishery yields.

Invertebrate declines are widespread in terrestrial ecosystems, and pesticide use is often cited as a causal factor. Here, we report that aquatic systems are threatened by the high toxicity and persistence of neonicotinoid insecticides. These effects cascade to higher trophic levels by altering food web structure and dynamics, affecting higher-level consumers. Using data on zooplankton, water quality, and annual fishery yields of eel and smelt, we show that neonicotinoid application to watersheds since 1993 coincided with an 83% decrease in average zooplankton biomass in spring, causing the smelt harvest to collapse from 240 to 22 tons in Lake Shinji, Shimane Prefecture, Japan. This disruption likely also occurs elsewhere, as neonicotinoids are currently the most widely used class of insecticides globally.

Occurrence and assessment of the risk of ultraviolet filters and light stabilizers in Victorian estuaries.

This reconnaissance study was undertaken to examine the occurrence of common ultraviolet filters (UVF) and light stabilizers (UVLS), and preservatives in four different estuaries in Port Philip Bay, Victoria, for the first time. In total, 11 UV filters, 10 UV stabilizers, 12 preservatives and a metabolite, and one fragrance were screened in grab samples of water and sediment using a combination of solid phase extraction and gas and liquid chromatography mass spectrometry measurement techniques. In that context, 16 of the UVF and UVLS and 5 of the preservatives screened were observed in water and/or sediment samples. There are no marine water quality guideline values for any of the fragrances, preservatives and UV filters and light stabilizers in Australia's current national water quality guidelines, so potential risk was assessed using the risk quotient (RQ) and toxic unit (TU) concepts. In that context, only two chemicals (OC and EHMC) had both an RQ above 1 and a log10TU above - 3, suggesting that few of the screened chemicals would have posed an individual, short-term risk to organisms in the waters studied at the time of sampling. However, the detection of common UV filters, such as 4MBC, EHMC, OC and the common preservatives 2-PE, MP, and PB in these Victorian estuaries highlights that the existence of personal care products in the environment is not just an issue for more densley populated countries in the northern hemisphere, but also potentially of concern in Australia. And, in that context, more sampling campaigns in Port Philip Bay are of paramount importance to assess the potential risk posed by these compounds to aquatic ecosystems.

Contribution of pharmaceuticals and personal care products (PPCPs) to whole toxicity of water samples collected in effluent-dominated urban streams.

Water samples were collected from effluent-dominated urban streams in Tokushima, Kyoto, and Saitama in Japan to roughly determine the contribution of pharmaceuticals and personal care products (PPCPs) and surfactants to whole toxicity of the water. Approximately 100 PPCPs including anionic surfactants such as linear alkylbenzene sulfonate (LAS), were chemically analyzed. Using 14 water samples, chronic or sub-chronic toxicity tests were conducted on three aquatic species, the green alga Raphidocelis subcapitata, the cladoceran Ceriodaphnia dubia, and the zebrafish Danio rerio. Bioassays for the selected individual PPCPs were conducted using the three species. Assuming the concentration addition (CA) model, the contribution of each PPCP to the whole toxicity of the riverwater was estimated based on toxicity unit (TU). The contribution of PPCPs, which primarily consists of a few antibiotic agents such as triclosan and clarithromycin, ranged from 0.9% to 69% of the whole toxicity of the water samples for algae, whereas the selected LAS congeners accounted for at most 5.3%. In contrast, the contribution of LAS ranged from 0.067% to 86% and from 0.021% to 27% of the whole toxicity for cladoceran and zebrafish, respectively, whereas that of PPCPs for these species was at most 2.1% at all sampling points. Our results suggest a limited contribution of PPCPs except for antimicrobial agents and the possible substantial contribution of LAS to toxicity in cladocerans and zebrafish.

Occurrence of preservatives and antimicrobials in Japanese rivers.

We established a method for the simultaneous analysis of seven preservatives and five antimicrobials in water. These chemicals are widely used in cosmetics, and their presence in river water is of concern. We used the method to test 13 sites in Japanese rivers and streams contaminated by domestic wastewater, effluent, or industrial wastewater. 2-Phenoxyethanol (2-PE), isopropylmethylphenol, resorcinol, and triclosan were detected at most sites; the maximum concentration of 2-PE detected was 14000 ng L(-1). The results suggest that the major sources of 2-PE were cosmetics and household detergents. The ratio of methylparaben to n-propylparaben in river waters with direct wastewater drainage was similar to that in common cosmetics. This is the first research on levels of 2-PE, isopropylmethylphenol, and chlorphenesin in river water.

Ecological risk assessment of urban creek sediments contaminated by untreated domestic wastewater: potential contribution of antimicrobials and a musk fragrance.

Despite the fact that some hydrophobic pharmaceuticals and personal care products (PPCPs) have been found to accumulate in river sediments, little is known about the contribution of these compounds to the toxicity of the whole sediment. We sampled river sediments from two urban creeks with an unsewered drainage area to investigate the toxicity for a benthic organism, Chironomus yoshimatsui. The concentrations of selected hydrophobic PPCPs, triclosan (TCS), triclocarban (TCC) and galaxolide (HHCB) were analysed using gas chromatographic mass spectroscopy or liquid chromatographic mass spectroscopy and were found to lie within the range 50 to 200 ng g(-1). The toxicity of the three individual contaminants for the chironomid was also determined. The toxicity of TCC was found to be the strongest, with an NOEC value of 2.5 microg g(-1). Combining the toxicity and measured environmental concentration, the ecological risk was assessed and the contribution of these contaminants to the whole sediment toxicity estimated, assuming additivity. The hazard quotient of all three compounds, determined without assessment factor, ranged between 0.01 and 0.1. The combined contribution of the three compounds to total sediment toxicity was as high as 8.2%, but other unknown factors may also make an important contribution.

Concentration of organic sun-blocking agents in seawater of beaches and coral reefs of Okinawa Island, Japan.

The concentration of UV filters (UVFs) and UV light stabilizers (UVLSs) were measured in seawater and river water collected from sites at four beaches, two reefs, and one river on Okinawa Island, Japan. UVFs and/or UVLSs of 8-10 types were detected in beaches samples and 6-9 types were detected in reef samples. The total UVF concentrations at the beach sites were highest either in July or August with a maximum of 1.4 µg L(-1). The concentrations at the reef sites did not show peaks in summer and the maximum values were close to 10 ng L(-1). The detected UVF profiles reflected the ingredients of sunscreens used in each region. The highest UVLS concentrations at the reefs were observed not only in summer but also in June and September. The UVLS concentrations at the reefs were similar to or even higher than that at the beaches or in the river.

Ecotoxicity and screening level ecotoxicological risk assessment of five antimicrobial agents: triclosan, triclocarban, resorcinol, phenoxyethanol and p-thymol.

Acute and chronic (or sub-chronic) toxicity of five selected antimicrobial agents, including triclosan (TCS), triclocarban (TCC), resorcinol, phenoxyethanol and p-thymol, was investigated using the conventional three-aquatic-organism battery. These compounds are widely used in cosmetics and other personal care products and their ecological risk has recently become a significant concern. As results of toxicity tests, TCS was found to be most strongly toxic for green algae [e.g. 72 h no observed effect concentration (NOEC) of 0.50 µg l(-1) ] among the selected compounds, followed by TCC, while TCC was more toxic or similar to TCS for Daphnia and fish (e.g. Daphnia 8 day NOEC of 1.9 µg l(-1) ). Having compared the predicted no effect concentration (PNEC) determined from the toxicity data with measured environmental concentrations (MEC), the preliminary ecological risk assessment of these five antimicrobials was conducted. The MEC/PNEC ratios of TCS and TCC were over 1 for some monitoring data, especially in urban streams with watershed areas without sewage service coverage, and their potential risk for green algae and Daphnia might be at a level of concern, although the contribution of TCS/TCC on the total toxicity of the those sites needs to be further investigated. For the three other antimicrobials, the maximum MEC/PNEC ratio for resorcinol was 0.1-1, but those for phenoxyethanol and p-thymol were <0.1 and their risk to aquatic organisms is limited, although the additive effects with TCS, TCC and other antimicrobial agents, such as parabens, need to be further examined in future studies.

Occurrence and profiles of organic sun-blocking agents in surface waters and sediments in Japanese rivers and lakes.

Sun-blocking agents including eight UV filters (UVF) and 10 UV light stabilizers (UVLS) were measured in water and sediment collected from 22 rivers, four sewage treatment plant effluents (STPE) and three lakes in Japan. Total sun blocking agents levels ranged from N.D. to 4928 ng/L and from 2.0 to 3422 µg/kg dry wt in surface water and in sediment, respectively. Benzyl salicylate, benzophenone-3, 2-ethyl hexyl-4-methoxycinnamte (EHMC) and octyl salicylate were dominant in surface water receiving wastewater effluents and STPE, although UV-328, benzophenone and EHMC were dominant in other surface water except background sites. Three UVF and nine UVLS were observed from all sediment and their compositions showed similar patterns with UV-328 and UV-234 as the most prevalent compounds. Homosalate, octocrylene, UV-326, UV-327, UV-328 and UV-234 were significantly correlated with Galaxolide® in sediments. Concentrations of UV-327 and UV-328 also had strong correlation between those of UV-326 in sediment.

Atmospheric polycyclic aromatic hydrocarbons: size distribution, estimation of their risk and their depositions to the human respiratory tract.

Polycyclic aromatic hydrocarbons (PAHs) in the atmosphere may be one of the causes of lung cancer. However, in many countries including Japan, only benzo[a]pyrene is regulated, though more toxic PAHs than benzo[a]pyrene have been reported. Therefore, it is necessary to characterize the risk of atmospheric PAHs and to find major contributing compounds that can act as suitable indicators for estimating and monitoring the risk of PAHs as a whole. The primary objectives of this study are to investigate the risk of 22 combined atmospheric PAHs and to find major contributing compounds that can act as adequate indicators for estimating the risk. The average lifetime cancer risk for all 22 PAHs in winter was 1.7 x 10(-4) in the Yokohama residential area. Although benzo[a]pyrene has been considered to be a useful indicator in many countries, the present study also showed that benzo[a]pyrene contributed only ca. 40% of the total cancer risk for all 22 PAHs, as calculated by unit risk. Six PAHs (dibenzo[a,h]anthracene, benzo[b]fluoranthene, indeno[1,2,3-cd]perylene, dibenzo[a,h]pyrene, dibenzo[a,e]pyrene, and benzo[a]pyrene) contributed 93% of the overall risk. Therefore, these six PAHs, including the high molecular ones, would be better indicators of the risk than benzo[a]pyrene alone. The secondary objective of this study is to reveal the PAHs that are major contributors to the deposition that contribute to the total deposition of PAHs in the human respiratory tract. The results revealed that the same six PAHs identified using unit risk evaluation were large contributors in all five parts of the respiratory tracts in adult males in spite of deposition process. It was concluded that the reason for this was that these six PAHs had the same size distributions, of which the 0.43-1.1 microm fraction was the most largest, about 57-70% of the whole concentration.