Characterization of Low-Molecular-Weight Dissolved Organic Matter Using Optional Dialysis and Orbitrap Mass Spectrometry.

Low-molecular-weight (LMW, <1000 Da) dissolved organic matter (DOM) plays a significant role in metal/organic pollutant complexation, as well as photochemical/microbiological processes in freshwater ecosystems. The micro size and high reactivity of LMW-DOM hinder its precise characterization. In this study, Suwannee River fulvic acid (SRFA), a commonly used reference material for aquatic DOM, was applied to examine the optical features and molecular composition of LMW-DOM by combining membrane separation, ultraviolet-visible absorption and Orbitrap mass spectrometry (MS) characterization. The 100-500 Da molecular weight cut-off (MWCO) membrane had a better performance in regard to separating the tested LMW-DOM relative to the 500-1000 Da MWCO membrane. The ultraviolet-visible absorbance decreased dramatically for the retentates, whereas it increased for the dialysates. Specifically, carbohydrates, lipids and peptides exhibited high selectivity to the 100-500 Da MWCO membrane in early dialysis. Lignins, tannins and condensed aromatic molecules displayed high permeability to the 500-1000 Da MWCO membrane in late dialysis. Overall, the retentates were dominated by aromatic rings and phenolic hydroxyls with high O/Cwa (weighted average of O/C) and low H/Cwa. Conversely, such dialysates had numerous aliphatic chains with high H/Cwa and low O/Cwa compared to SRFA. In particular, LMW-DOM below 200 Da was identified by Orbitrap MS. This work provides an operational program for identifying LMW-DOM based on the SRFA standard and MS analysis.

Particulate and Dissolved Black Carbon in Coastal China Seas: Spatiotemporal Variations, Dynamics, and Potential Implications.

Elaborating the spatiotemporal variations and dynamic mechanisms of black carbon (BC) in coastal seas, the geographically pivotal intermediate zones that link the terrestrial and open oceanic ecosystems, will contribute significantly to refine the regional and global BC geochemistry. In this study, we implemented a large spatial-scale and multiseason and -layer seawater sampling campaign in high BC emission influenced coastal China seas (Bohai Sea and Northern Yellow Sea) and quantified the thermal/optical reflectance-based particulate BC (PBC) and benzene polycarboxylic acids-based dissolved BC (DBC). We found that the climate and its associated hydrological effects (including the intensive resuspension and coastal current transport) largely regulate both PBC and DBC spatiotemporal variations and dynamics. In combination with previous work on upstream rivers and downstream open ocean, a significant and continuous decrease in the DBC aromatic condensation was observed along the river-to-ocean continuum, probably due to the increment of the photochemical degradation during the waterborne transport. Based on our DBC methodological development, i.e., the determination and subsequent inclusion of the nitrated BC molecular markers, the magnitudes of the current global DBC fluxes and pools were updated. After the update, the DBC fluxes from atmospheric deposition and riverine delivery were estimated at rates of 4.3 and 66.3 Tg yr-1, respectively, and the global oceanic DBC pool was approximately 36 Gt. This update will greatly assist in constructing a more robust regional and global DBC and BC cycling and budgets.

Economic benefit of ecological remediation of mercury pollution in southwest China 2007-2022.

Methylmercury (MeHg) exposure via rice consumption poses health risk to residents in mercury contaminated areas, such as the Wanshan Hg mining area (WSMA) in southwest China. Making use of the published data for WSMA, this study developed a database of rice MeHg concentrations for different villages in this region for the years of 2007, 2012, 2017, and 2019. The temporal changes of human MeHg exposure, health effects, and economic benefits under different ecological remediation measures were then assessed. Results from this study revealed a decrease of 3.88 µg/kg in rice MeHg concentration and a corresponding reduction of 0.039 µg/kg/d in probable daily intake of MeHg in 2019 compared to 2007 on regional average in the WSMA. Ecological remediation measures in this region resulted in the accumulated economic benefits of $38.7 million during 2007-2022, of which 84 % was from pollution source treatment and 16 % from planting structure adjustment. However, a flooding event in 2016 led to an economic loss of $2.43 million (0.38 % of regional total Gross Domestic Product). Planting structure adjustment generates the greatest economic benefits in the short term, whereas pollution source treatment maximizes economic benefits in the long term and prevents the perturbations from flooding event. These findings demonstrate the importance of ecological remediation measures in Hg polluted areas and provide the foundation for risk assessment of human MeHg exposure via rice consumption.

Describing the toxicity and sources and the remediation technologies for mercury-contaminated soil.

Mercury (Hg) is a natural element and its compounds are found as inorganic and organic forms in the environment. The different Hg forms (e.g., methylmercury (MeHg)), are responsible for many adverse health effects, such as neurological and cardiovascular effects. The main source of Hg is from natural release. Nevertheless, with the development of industrialization and urbanization, Hg-contaminated soil mainly influenced by human activities (especially near mercury mining areas) has become a problem. Therefore, much more attention has been paid to the development and selection of various treatment methods to remediate Hg-contaminated soils. This paper presented a systematical review of the recent developments for the remediation of Hg-contaminated soils. Firstly, we briefly introduced the Hg chemistry, toxicity and the main human activity-related sources of mercury in soil. Then the advances in remediation technologies for removing Hg pollution from the soil were summarized. Usually, the remediation technology includes physical, chemical and biological remediation technology. Depending on this, we further classified these remediation technologies into six techniques, including thermal desorption, electrokinetic extraction, soil washing, chemical stabilization, phytoremediation and microbial technology. Finally, we also discussed the challenges and future perspectives of remediating Hg-contaminated soils.

Occurrence and spatial distribution of organophosphorus flame retardants and plasticizers in the Bohai and Yellow Seas, China.

Seawater samples from 50 sites in the BS and YS were collected to investigate the spatial distribution of 7 OPs. Concentrations of the total OPs (Æ©OPs) in the BS and YS ranged from 8.12ngL-1 to 98.04ngL-1 with a geometric mean (GM) of 23.70ngL-1. Tris(1-chloro-2-propyl) phosphate (TCPP) was the dominant compound, followed by tris(2-chloroethyl) phosphate (TCEP) and triphenylphosphine oxide (TPPO). The Æ©OPs together with the most commonly detected individual OPs (TCPP, TCEP, tris(1,3-dichloro-2-propyl) phosphate (TDCPP), tri-iso-butyl phosphate (TiBP), triphenyl phosphate (TPhP), and TPPO) tended to decrease from nearshore to offshore and from the surface to the bottom seawaters, indicating major land-based sources. Furthermore, the Yellow Sea Cold Water Mass (YSCWM), Changjiang Diluted Water (CDW), Taiwan Warm Current (TaWC), and Subei Coastal Water (SCW) influenced the horizontal and vertical distributions of the OPs in the study area.

GIS-based health assessment of the marine ecosystem in Laizhou Bay, China.

According to 2014-2016 monitoring data, an assessment index system including water quality, depositional environment and ecosystem was built to evaluate the health statue of marine ecosystem in the Laizhou Bay using analytic hierarchy process (AHP) method. The results, spatialized in ArcGIS software, show: while the comprehensive ecological health index is 0.62, the ecological environmental quality in the Laizhou Bay is in a sub-healthy state; the unhealthy area is mainly concentrated in southwestern inshore region, and impacted by serious environmental problems, such as water eutrophication and heavy metal pollution; the northwestern and southeastern inshore regions are in a sub-healthy state, while the eastern inshore and northern areas are in the healthiest state. The land-based pollutants that discharge into the sea may be the leading factors that are causing ecological environment deterioration in the Laizhou Bay, and the reclamation work ongoing around the port has exacerbated the ecological risk.

Polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants (aBFRs) in sediments from four bays of the Yellow Sea, North China.

The distribution characteristics and potential sources of polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants (aBFRs) were investigated in 54 surface sediment samples from four bays (Taozi Bay, Sishili Bay, Dalian Bay, and Jiaozhou Bay) of North China's Yellow Sea. Of the 54 samples studied, 51 were collected from within the four bays and 3 were from rivers emptying into Jiaozhou Bay. Decabromodiphenylethane (DBDPE) was the predominant flame retardant found, and concentration ranged from 0.16 to 39.7 ng g(-1) dw and 1.13-49.9 ng g(-1) dw in coastal and riverine sediments, respectively; these levels were followed by those of BDE 209, and its concentrations ranged from n.d. to 10.2 ng g(-1) dw and 0.05-7.82 ng g(-1) dw in coastal and riverine sediments, respectively. The levels of DBDPE exceeded those of decabromodiphenyl ether (BDE 209) in most of the samples in the study region, whereas the ratio of DBDPE/BDE 209 varied among the four bays. This is indicative of different usage patterns of brominated flame retardants (BFRs) and also different hydrodynamic conditions among these bay areas. The spatial distribution and composition profile analysis indicated that BFRs in Jiaozhou Bay and Dalian Bay were mainly from local sources, whereas transport from Laizhou Bay by coastal currents was the major source of BFRs in Taozi Bay and Sishili Bay. Both the ∑PBDEs and ∑aBFRs (sum of pentabromotoluene (PBT), 2,3-diphenylpropyl-2,4,6-tribromophenyl ether (DPTE), pentabromoethylbenzene (PBEB), and hexabromobenzene (HBB)) were at low concentrations in all the sediments. This is probably attributable to a combination of factors such as low regional usage of these products, atmospheric deposition patterns, coastal currents transportation patterns, and degradation processes for higher BDE congeners. This paper is the first study that has investigated the levels of DBDPE in the coastal sediments of China's Yellow Sea.

Radiocarbon-based impact assessment of open biomass burning on regional carbonaceous aerosols in North China.

Samples of total suspended particulates (TSPs) and fine particulate matter (PM2.5) were collected from 29th May to 1st July, 2013 at a regional background site in Bohai Rim, North China. Mass concentrations of particulate matter and carbonaceous species showed a total of 50% and 97% of the measured TSP and PM2.5 levels exceeded the first grade national standard of China, respectively. Daily concentrations of organic carbon (OC) and elemental carbon (EC) were detected 7.3 and 2.5 µg m(-3) in TSP and 5.2 and 2.0 µg m(-3) in PM2.5, which accounted 5.8% and 2.0% of TSP while 5.6% and 2.2% for PM2.5, respectively. The concentrations of OC, EC, TSP and PM2.5 were observed higher in the day time than those in the night time. The observations were associated with the emission variations from anthropogenic activities. Two merged samples representing from south and north source areas were selected for radiocarbon analysis. The radiocarbon measurements showed 74% of water-insoluble OC (WINSOC) and 59% of EC in PM2.5 derived from biomass burning and biogenic sources when the air masses were from south region, and 63% and 48% for the air masses from north, respectively. Combined with backward trajectories and daily burned area, open burning of agricultural wastes was found to be predominating, which was confirmed by the potential source contribution function (PSCF).

Identification and quantification of shipping emissions in Bohai Rim, China.

Rapid development of port and shipbuilding industry in China has badly affected the ambient air quality of coastal zone due to shipping emissions. A total of 60 ambient air samples were collected from background site of Tuoji Island in Bohai Sea strait. The air samples were analyzed for PM2.5, organic carbon (OC), element carbon (EC), inorganic elements, and water-soluble ions. The maximum concentration of PM2.5 was observed during spring (73.6 µg·m(-3)) compared to winter (39.0 µg·m(-3)) with mean of 54.6 µg·m(-3). Back trajectory air mass analysis together with temporal distribution of vanadium (V) showed that V could be the typical tracer of shipping emissions at Tuoji Island. Furthermore, the ratios of vanadium to nickel (V/Ni), vanadium to lead (V/Pb) and vanadium to zinc (V/Zn) also suggest shipping emissions at Tuoji Island. The annual average primary PM2.5 estimate of shipping emissions was 0.65 µg·m(-3) at Tuoji Island, accounting for 2.94% of the total primary PM2.5, with a maximum of 3.16% in summer and a minimum of 2.39% in autumn.

Impact of agricultural waste burning in the Shandong Peninsula on carbonaceous aerosols in the Bohai Rim, China.

A total of 11 5PM2.5 samples were collected for analyzing organic carbon (OC) and elemental carbon (EC) at Tuoji Island (TI), China from November 2011 to December 2012. The results showed that annual arithmetical means of OC and EC concentrations were 3.8 ± 2.7 and 2.2 ± 2.2 µg m(-3), which contributed 8% and 4% of PM2.5 mass concentrations, respectively. High EC concentrations occurred in winter, contributed mainly by EC outflow from the northwest source region, while high OC concentrations were found during spring, attributed largely to biofuel burning in the Shandong Peninsula, and short distance and favorable transport from the peninsula to the TI. Agricultural waste open burning in the peninsula caused the largest variability of OC concentration in summer. Eliminating agricultural field burning in the peninsula can reduce at least one-third of concentration levels and half of northward transport fluxes of OC and EC in Bohai Rim in summer.

[Stable carbon isotope of black carbon from typical emission sources in China].

Smoke particles from the three typical BC emission sources (biomass burning, household coal combustion, and vehicular exhaust) were collected and analyzed for stable carbon isotopes (delta13C) of black carbon (BC), total carbon (TC), as well as the original fuels. The results show that corn stalk (a typical C4 plant, -13.62 per thousand) has the highest delta13C(BC) value, and the average values for C3 plants, bituminous coals, and vehicle exhaust are -26.49 per thousand +/- 1.17 per thousand, -23.46 per thousand +/- 0.37 per thousand, and -25.17 per thousand +/- 0.40 per thousand, respectively. delta13C(BC) values from the three sources are similar to the corresponding fuels, and the ranges of these values are different from each other. Carbon fractionation occurs during the process of BC formation. delta13C(BC) for C4 plant (corn stalk) is lower than that of the fuel by 1.62 per thousand, while the values for C3 plants and coals are higher than that of the fuels by 0.63 per thousand and 0.52 per thousand, respectively. CTO-375 method, which is used to extract BC from TC, affects the stable carbon isotope of smokes from biomass burning to some extent (the difference between delta13C(BC) and delta13C(TC) is nearly 0.50 per thousand), but has little effect on fossil fuel smokes. This delta13C database for typical emission sources provides scientific information on BC source apportionment.