A 75-year history of microplastic fragment accumulation rates in a semi-enclosed hypoxic basin.

Plastic budgets in the marine environment and their long-term trends are yet to be fully understood. Measuring the accumulation rates in bottom sediments is crucial to solving the riddle of missing ocean plastics. Previous studies based on coastal sediment cores have found that accumulation rates have increased with increases in plastic production and/or regional populations. However, the correlations between the rates and bioactivities or ocean dynamics, which are crucial for modeling the microplastic sinking process, have not been examined. We revealed a 75-year microplastic fragment (0.3-5.0 mm) accumulation rate history in a hypoxic basin, Beppu Bay, Japan, based on multi-core analysis and 210Pb dating of the sediment which was cross-checked by time control with 137Cs radioactivity peaks. We found that a long-term linear increasing trend with an approximately 20-year variation overlapped with significant peaks around 1990 and 2014 with the first polypropylene microplastic fragment detected from a 1958.8-1961.0 CE sediment layer. The maximum rate was 203 pieces m-2 y-1 with an abundance of 86 pieces kg-1-dry in 2014. Smaller fragments in the size range of 0.3-2.0 mm have been consistently dominant in terms of the accumulation rate throughout the 1955-2015 period, accounting for 85.3 % of the total accumulation rate. The three major polymers (polyethylene, polypropylene, and polystyrene) accounted for 96.6 % of the total rate. The rate was highly and positively correlated with the chlorophyll-a accumulation rate and concentration in the sediment. Based on the microplastic accumulation rates and concentration in the seawater, the mean sinking velocity of microplastics was estimated to be in the order of 101 m d-1. Our results will contribute to significant progress in modeling the microplastic sinking process by offering the first field measurement-based mean sinking velocity and significant correlations between the rate and bioactivity-related signals.

Reconstruction of 100-year dynamics in Daphnia spawning activity revealed by sedimentary DNA.

Environmental DNA (eDNA) is currently developing as a powerful tool for assessing aquatic species dynamics. However, its utility as an assessment tool for quantification remain under debate as the sources of eDNA for different species is not always known. Therefore, accumulating information about eDNA sources from different species is urgently required. The objective of our study was to evaluate whether sedimentary DNA targeting two Daphnia species, D. galeata and D. pulicaria, could track Daphnia population dynamics and resting egg production. Applying a quantitative PCR targeting the mitochondrial 12S rRNA gene on sediment cores collected in Lake Biwa, Japan, we compared sedimentary DNA concentration of Daphnia with the abundance of remains and ephippia, reflecting their abundance and resting egg production, respectively. We found that the sedimentary DNA concentrations of Daphnia for the past century were inconsistent with their population abundance. However, the concentration was highly correlated with the resting egg production. Our results provide evidence that ephippia with resting eggs, released during spawning activities, was a significant source of Daphnia DNA archived in sediments. Our work provides critical insights for using sedimentary DNA as a monitoring tool for egg production dating back 100 years.

Historical record of polychlorinated biphenyls in a sediment core from Lake Biwa, Japan: Significance of unintentional emission and weathering signals revealed by full congener-specific analysis.

The occurrence of 209 PCB congeners was determined in a sediment core dated between 1930 and 2019 from Lake Biwa, a typical temperate monomictic lake in Japan. Concentrations of total PCBs ranged from 5.3 to 48 ng/g dry weight (dw), showing a highest peak at the 1960s to 1970s. The temporal trend of total PCBs in this sediment core generally matched with Japanese PCB production and emission pattern (i.e., increasing from the 1950s, peaking at 1970, and gradually decreasing since 1972). The vertical PCB profiles in our core were affected by physical mixing and bioturbation. By using a detailed and comprehensive analytical method, we have found elevated concentrations and special historical profiles of several congeners such as CB-7, -11, -47/48/75, -51, -68, and -209, which are still rarely included in routine PCB analysis. Some tetra-CB congeners like CB-47/48/75, -51, and -68 showed their concentration peaks at the early 2010s, which may be unintentionally produced during polymer manufacturing processes. PCB homolog- and congener-specific profiles in our sediment core samples have experienced weathering with higher proportions of penta- and hexa-CBs as compared to the Kanechlor usage pattern (i.e., dominated by tri- and tetra-CBs). Both intentional (i.e., technical mixtures) and unintentional (e.g., PCB-containing polymers and pigments) sources of PCBs were suggested from congener-specific analysis.

Determination of brominated flame retardants including polybrominated diphenyl ethers, pentabromoethylbenzene, hexabromobiphenyl, and decabromodiphenyl ethane in sediment samples: Validation of a rapid and efficient clean-up method and application to a sediment core from Lake Biwa, Japan.

The development of rapid and efficient analytical method for the determination of legacy and current-use brominated flame retardants (BFRs) has been performed due to environmental concern related to these pollutants. In the present study, we used an automated clean-up device equipped with pre-packed micro-column sets (containing sulfuric acid impregnated silica gel and silver-modified alumina) to develop an effective purification method for polybrominated diphenyl ethers (PBDEs), pentabromoethylbenzene, hexabromobiphenyl, and decabromodiphenyl ethane (DBDPE) in sediment extracts. Matrix-spiked sediments (n = 6) and the Standard Reference Material® 1944 samples (n = 6) were tested. Our method showed acceptable accuracy, repeatability, and sensitivity for almost all the target compounds with reduced processing time, labor requirement, and solvent amounts as compared to conventional clean-up method (e.g., sulfuric acid treatment and self-packed chromatographic columns). The validated method was applied to sediment core samples (n = 16) collected in 2019 from Lake Biwa, the largest lake in Japan. PBDEs were detected in sediment samples of 0-13 cm depth (dated between 1990 and 2019) at relatively low concentrations (median 5.7; range 2.6-9.4 ng/g dry weight). PBDE profiles were dominated by BDE-209, which accounted for 91 ± 10% of total PBDEs. Among other BFRs, only DBDPE was found in sediment layers of 0-9 cm depth (deposited between 2005 and 2019). DBDPE concentrations ranged from 0.43 to 1.6 (median 0.71) ng/g and showed increasing trend toward shallower depths.

Historical changes in the ecosystem condition of a small mountain lake over the past 60 years as revealed by plankton remains and Daphnia ephippial carapaces stored in lake sediments.

To examine if changes in species composition of a plankton community in the past due to anthropogenic activities can be clarified in lakes without any monitoring data, we analyzed genetically ephippial carapaces of Daphnia with plankton remains stored in the bottom sediments of Lake Hataya Ohunma in Japan. In the lake, abundance of most plankton remains in the sediments was limited and TP flux was at low levels (2-4 mg/m2/y) before 1970. However TP flux increased two-fold during the period from 1980s to 1990 s. In parallel with this increase, abundance of most plankton remains increased although abundance of benthic testate amoebae's remains decreased, indicating that the lake trophic condition had changed from oligo- to mesotrophic for the past 60 years. According to cluster analysis, the stratigraphic sediments were divided into two periods with different features of the phytoplankton composition. Chronological comparison with events in the watershed suggested that eutrophication occurred because of an increase in visitors to the watershed and deposition of atmospheric dust. In this lake more than 50% of resting eggs produced by Daphnia over the past 60 years hatched. However, genetic analysis of the ephippial carapaces (remains) showed that the Daphnia population was originally composed of D. dentifera but that D. galeata, or its hybrid with D. dentifera, invaded and increased the population density when the lake was eutrophied. Subsequently, large D. pulex established populations in the 1980s when largemouth bass were anonymously introduced. These results indicated that the Lake Hataya Ohunma plankton community underwent significant changes despite the fact that there were no notable changes in land cover or land use in the watershed. Since increases in atmospheric deposition and release of fish have occurred in many Japanese lakes, the changes in the plankton community described here may be widespread in these lakes.

Sedimentary records of metal deposition in Japanese alpine lakes for the last 250 years: recent enrichment of airborne Sb and In in East Asia.

Concentrations of 18 elements, including Sb, In, Sn, and Bi, were measured in sediment cores from two pristine alpine lakes on Mount Hachimantai, northern Japan, representing the past 250 years. Vertical variations in concentrations are better explained by atmospheric metal deposition than by diagenetic redistribution of Fe and Mn hydroxide and organic matter. Anthropogenic metal fluxes were estimated from (210)Pb-derived accumulation rates and metal concentrations in excess of the Al-normalized mean background concentration before 1850. Anthropogenic fluxes of Sb and In showed gradual increases starting around 1900 in both lakes, and marked increases after 1980. Comparison of Sb/Pb and Pb stable isotope ratios in sediments with those in aerosols of China or northern Japan and Japanese source materials (recent traffic- and incinerator-derived dust) suggest that the markedly elevated Sb flux after 1980 resulted primarily from enhanced long-range transport in aerosols containing Sb and Pb from coal combustion on the Asian continent. The fluxes of In, Sn, and Bi which are present in Chinese coal showed increasing trends similar to Sb for both study lakes. This suggests that the same source although incinerators in Japan may not be ruled out as sources of In. The sedimentary records for the last 250 years indicate that atmospheric pollution of Sb and In in East Asia have intensified during recent decades.

Changes in stable isotopes, lignin-derived phenols, and fossil pigments in sediments of Lake Biwa, Japan: implications for anthropogenic effects over the last 100 years.

We measured stable nitrogen (N) and carbon (C) isotope ratios, lignin-derived phenols, and fossil pigments in sediments of known ages to elucidate the historical changes in the ecosystem status of Lake Biwa, Japan, over the last 100 years. Stable N isotope ratios and algal pigments in the sediments increased rapidly from the early 1960s to the 1980s, and then remained relatively constant, indicating that eutrophication occurred in the early 1960s but ceased in the 1980s. Stable C isotope ratios of the sediment increased from the 1960s, but decreased after the 1980s to the present. This decrease in stable C isotope ratios after the 1980s could not be explained by annual changes in either terrestrial input or algal production. However, when the C isotope ratios were corrected for the Suess effect, the shift to more negative isotopic value in atmospheric CO(2) by fossil fuel burning, the isotopic value showed a trend, which is consistent with the other biomarkers and the monitoring data. The trend was also mirrored by the relative abundance of lignin-derived phenols, a unique organic tracer of material that originated from terrestrial plants, which decreased in the early 1960s and recovered to some degree in the 1980s. We detected no notable difference in the composition of lignin phenols, suggesting that the terrestrial plant composition did not change markedly. However, we found that lignin accumulation rate increased around the 1980s. These results suggest that although eutrophication has stabilized since the 1980s, allochthonous organic matter input has changed in Lake Biwa over the past 25 years.