Stable Isotopic and Metagenomic Analyses Reveal Microbial-Mediated Effects of Microplastics on Sulfur Cycling in Coastal Sediments.

Microplastics are readily accumulated in coastal sediments, where active sulfur (S) cycling takes place. However, the effects of microplastics on S cycling in coastal sediments and their underlying mechanisms remain poorly understood. In this study, the transformation patterns of different S species in mangrove sediments amended with different microplastics and their associated microbial communities were investigated using stable isotopic analysis and metagenomic sequencing. Biodegradable poly(lactic acid) (PLA) microplastics treatment increased sulfate (SO42-) reduction to yield more acid-volatile S and elementary S, which were subsequently transformed to chromium-reducible S (CRS). The S isotope fractionation between SO42- and CRS in PLA treatment increased by 9.1‰ from days 0 to 20, which was greater than 6.8‰ in the control. In contrast, recalcitrant petroleum-based poly(ethylene terephthalate) (PET) and polyvinyl chloride (PVC) microplastics had less impact on the sulfate reduction, resulting in 7.6 and 7.7‰ of S isotope fractionation between SO42- and CRS from days 0 to 20, respectively. The pronounced S isotope fractionation in PLA treatment was associated with increased relative abundance of Desulfovibrio-related sulfate-reducing bacteria, which contributed a large proportion of the microbial genes responsible for dissimilatory sulfate reduction. Overall, these findings provide insights into the potential impacts of microplastics exposure on the biogeochemical S cycle in coastal sediments.

Molecular Characterization of Nitrogen-Containing Compounds in Humic-like Substances Emitted from Biomass Burning and Coal Combustion.

N-containing organic compounds (NOCs) in humic-like substances (HULIS) emitted from biomass burning (BB) and coal combustion (CC) were characterized by ultrahigh-resolution mass spectrometry in the positive electrospray ionization mode. Our results indicate that NOCs include CHON+ and CHN+ groups, which are detected as a substantial fraction in both BB- and CC-derived HULIS, and suggest that not only BB but also CC is the potential important source of NOCs in the atmosphere. The CHON+ compounds mainly consist of reduced nitrogen compounds with other oxygenated functional groups, and straw- and coal-smoke HULIS exhibit a lower degree of oxidation than pine-smoke HULIS. In addition, the NOCs with higher N atoms (N2 and/or N3) generally bear higher modified aromaticity index (AImod) values and are mainly contained in BB HULIS, especially in straw-smoke HULIS, whereas the NOCs with a lower N atom (N1) always have relatively lower AImod values and are the dominant NOCs in CC HULIS. These findings imply that the primary emission from CC may be a significant source of N1 compounds, whereas high N number (e.g., N2-3) compounds could be associated with burning of biomass materials. Further study is warranted to distinguish the NOCs from more sources.

Abundance and Light Absorption Properties of Brown Carbon Emitted from Residential Coal Combustion in China.

Brown carbon (BrC) fractions, including water-soluble organic carbon (WSOC), water-soluble humic-like substances (HULISw), alkaline soluble organic carbon (ASOC), and methanol soluble organic carbon (MSOC) were extracted from particles emitted from the residential combustion of coal with different geological maturities. The abundances and light absorption properties of these BrC fractions were comprehensively studied. The results showed that the abundances of the different constituents of the BrC fraction varied greatly with the extraction solvent, accounting for 4.3%-46%, 2.3%-23%, 3.2%-14%, and 76%-98% of the total carbon content in particles. The specific UV-vis absorbance (SUVA254) of BrC fractions followed the order of MSOC > ASOC > HULISw > WSOC. The WSOC and MSOC fractions from the combustion of low maturity coal had relatively low SUVA254 and high SR values. The mass absorption efficiencies (MAE365) for ASOC and MSOC were higher than for WSOC, and WSOC and MSOC from low maturity coal combustion had relatively low levels of light absorption. These findings indicated that coal combustion is a potential source of atmospheric BrC and the abundance and light absorption of the coal combustion-derived BrC fractions were strongly dependent on the extraction methods used and the coal maturity rather than the coal shapes.

Molecular Characterization of Water- and Methanol-Soluble Organic Compounds Emitted from Residential Coal Combustion Using Ultrahigh-Resolution Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

Water-soluble organic compounds (WSOC) and methanol-soluble organic compounds (MSOC) in smoke particles emitted from residential coal combustion were characterized by ultrahigh-resolution mass spectrometry. The results showed that the molecular compositions of WSOC and MSOC are different. S-containing compounds (CHOS and CHONS) are found to be the dominant components (65-87%) of the WSOC, whereas CHO and CHON compounds make a great contribution (79-96%) to the MSOC samples. It is worth noting that greater abundance of S-containing compounds was found in smoke produced from coal combustion compared to biomass burning and atmospheric samples. The molecular compositions of WSOC and MSOC also varied significantly depending on the maturity of the coal. The WSOC and MSOC derived from the combustion of low-maturity coal contained a higher proportion of oxidized functional groups but with a lower degree of aromaticity than the compounds derived from the combustion of high-maturity coal. Our findings suggest that organic molecules with a high modified aromaticity index, low O/C ratio, and low polarity showed stronger light absorption. This study also suggests that CHO and CHON compounds significantly contributed to the light absorption of WSOC and MSOC and that the contribution of CHON may be stronger.

Carbon isotope analyses of n-alkanes released from rapid pyrolysis of oil asphaltenes in a closed system.

RATIONALE: Carbon isotope analysis of n-alkanes produced by the pyrolysis of oil asphaltenes is a useful tool for characterizing and correlating oil sources. Low-temperature (320-350°C) pyrolysis lasting 2-3 days is usually employed in such studies. Establishing a rapid pyrolysis method is necessary to reduce the time taken for the pretreatment process in isotope analyses. METHODS: One asphaltene sample was pyrolyzed in sealed ampoules for different durations (60-120 s) at 610°C. The δ(13) C values of the pyrolysates were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The molecular characteristics and isotopic signatures of the pyrolysates were investigated for the different pyrolysis durations and compared with results obtained using the normal pyrolysis method, to determine the optimum time interval. Several asphaltene samples derived from various sources were analyzed using this method. RESULTS: The asphaltene pyrolysates of each sample were similar to those obtained by the flash pyrolysis method on similar samples. However, the molecular characteristics of the pyrolysates obtained over durations longer than 90 s showed intensified secondary reactions. The carbon isotopic signatures of individual compounds obtained at pyrolysis durations less than 90 s were consistent with those obtained from typical low-temperature pyrolysis. Several asphaltene samples from various sources released n-alkanes with distinct carbon isotopic signatures. CONCLUSIONS: This easy-to-use pyrolysis method, combined with a subsequent purification procedure, can be used to rapidly obtain clean n-alkanes from oil asphaltenes. Carbon isotopic signatures of n-alkanes released from oil asphaltenes from different sources demonstrate the potential application of this method in 'oil-oil' and 'oil-source' correlations. Copyright © 2016 John Wiley & Sons, Ltd.

Regional characteristics of atmospheric δ34S-SO42- over three parts of Asia monitored by quartz wool-based passive samplers.

A new method is presented for measuring atmospheric contents and δ34S-SO42- in airborne particulate matter using quartz wool disk passive air samplers (Pas-QW). The ability of Pas-QW samplers to provide time-integrated measurements of atmospheric SO42- was confirmed in a field calibration study. The average sampling rate of SO42- measured was 2.3 ± 0.3 m3/day, and this was not greatly affected by changes in meteorological parameters. The results of simultaneous sampling campaign showed that the average SO42- contents in Pakistan and the Indochina Peninsula (ICP) were relatively lower than that of China. The spatial distribution of SO42- concentrations was largely attributed to the development of the regional economies. The range of δ34S values observed in Pakistan (4.3 ± 1.4‰) and the ICP (4.5 ± 1.2‰) were relatively small, while a large range of δ34S values was observed in China (3.9 ± 2.5‰). The regional distribution of sulfur isotope compositions was significantly affected by coal combustion. A source analysis based on a Bayesian mixing model showed that 80.4 ± 13.1% and 19.6 ± 13.1% of artificial sulfur dioxide (SO2) sources in China could be attributed to coal combustion and oil combustion, respectively. The two sources differed greatly between regions, and the contribution of oil combustion in cities was higher than previously reported data obtained from emission inventories. This study confirmed that the Pas-QW is a promising tool for simultaneously monitoring atmospheric δ34S-SO42- over large regions, and that the results of the isotope models can provide a reference for the compilation of SO2 emission inventories.

Distribution and sources of DDT and its metabolites in porewater and sediment from a typical tropical bay in the South China Sea.

Dichlorodiphenyltrichloroethane (DDT) is well known for its harmful effects and has been banned around the world. However, DDT is still frequently detected in natural environments, particularly in aquaculture and harbor sediments. In this study, 15 surface sediment samples were collected from a typical tropical bay (Zhanjiang Bay) in the South China Sea, and the levels of DDT and its metabolites in sediment and porewater samples were investigated. The results showed that concentrations of DDXs (i.e., DDT and its metabolites) in bulk sediments were 1.58-51.0 ng g-1 (mean, 11.5 ng g-1). DDTs (DDT and its primary metabolites, dichlorodiphenyldichloroethane (DDD) and dichlorodiphenyldichloroethylene (DDE)) were the most prominent, accounting for 73.2%-98.3% (86.1% ± 12.8%) of the DDXs. Additionally, high-order metabolites (i.e., 1-chloro-2,2-bis(4'-chlorophenyl)ethylene (p,p'-DDMU), 2,2-bis(p-chlorophenyl)ethylene (p,p'-DDNU), 2,2-bis(p-chlorophenyl)ethanol (p,p'-DDOH), 2,2-bis(p-chlorophenyl)methane (p,p'-DDM), and 4,4'-dichlorobenzophenone (p,p'-DBP)) were also detected in most of the sediment and porewater samples, with DDMU and DBP being predominant. The DDTs concentration differed among the sampling sites, with relatively high DDTs concentrations in the samples from the aquaculture zone and an area near the shipping channel and the Haibin shipyard. The DDD/DDE ratios indicated a reductive dichlorination of DDT to DDD under anaerobic conditions at most of the sampling sites of Zhanjiang Bay. The possible DDT degradation pathway in the surface sediments of Zhanjiang Bay was p,p'-DDT/p,p'-DDD(p,p'-DDE)/p,p'-DDMU/p,p'-DDNU/ … /p,p'-DBP. The DDXs in the sediments of Zhanjiang Bay were mainly introduced via mixed sources of industrial DDT and dicofol, including fresh input and historical residue. The concentrations of DDXs in porewater samples varied from 66.3 to 250 ng L-1, exhibiting a distribution similar to that in the accompanying sediments. However, the content of high-order metabolites was relatively lower in porewater than in sediment, indicating that high-order degradation mainly occurs in particles. Overall, this study helps in understanding the distribution, source, and degradation of DDT in a typical tropical bay.

Gas chromatography/combustion/isotope ratio mass spectrometric analysis of the stable carbon composition of tetrols.

The stable carbon isotope compositions of tetrols, erythritol and threitol were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Using four tetrols with various delta(13)C values derivatized by methylboronic acid, the carbon isotope analysis method achieved excellent reproducibility and high accuracy. There was no carbon isotopic fractionation during the derivatization processes. The differences in the carbon isotopic compositions of methylboronates between the measured and calculated ranged from -0.20 to 0.12 per thousand, within the specification of the GC/C/IRMS system. It was demonstrated that delta(13)C values of tetrols could be calculated by a simple mass balance equation between tetrols, methylboronic acid, and methylboronates. The analogous 2-methyltetrols, marker compounds of photooxidation products of atmospheric isoprene, should have similar behavior using the same derivatization reagent. This method may provide insight on sources and sinks of atmospheric isoprene.

Influence of pyrolysis temperature and feedstock on carbon fractions of biochar produced from pyrolysis of rice straw, pine wood, pig manure and sewage sludge.

In this study, the influences of feedstock and pyrolysis temperature on carbon fractions of biochar were investigated. Four types of organic wastes (rice straw (RS), pine wood (PW), pig manure (PM) and sewage sludge (SS)) were pyrolyzed at different temperatures (300 °C, 400 °C, 500 °C, 600 °C and 700 °C). Biochar produced at low temperature exhibited high yields, high dissolved organic carbon (DOC) content and unstable organic carbon content. In contrast, biochar formed at high temperature showed high C content and C stability with a low O/C and H/C ratios. In addition, the biochar pyrolyzed from PW contained the lowest DOC of the four biochar types. The properties of DOC fractions (F1, F2 and F3) released from biochar differed depending on feedstock, pyrolysis temperatures, and extraction procedures. The highest specific ultraviolet absorbance at 254 nm of the F1 and F2 fractions were observed for RS biochar, suggesting that more aromatic organic matter was present in sequentially extracted fractions of RS biochar than in extracts from the other biochars. In addition, the hot water extracts (F2) mostly showed higher aromaticity than cold water extracts (F1). The stability of biochars was greatly enhanced at pyrolysis temperatures >500 °C. If the biochars produced in this study were to be used for carbon sequestration in soil, the first priority should be PW, followed in order by RS and PM.

Gas chromatography flow rates for determining deuterium/hydrogen ratios of natural gas by gas chromatography/high-temperature conversion/isotope ratio mass spectrometry.

The effects of the gas chromatography flow rate on the determination of the deuterium/hydrogen (D/H) ratios of natural gas utilising gas chromatography/high-temperature conversion/isotope ratio mass spectrometry (GC/TC/IRMS) have been evaluated. In general, the measured deltaD values of methane, ethane and propane decrease with increase in column flow rate. When the column flow rate is 1 mL/min or higher, which is commonly used for the determination of D/H ratios of natural gas, the organic H in gas compounds may not be completely converted into hydrogen gas. Based on the results of experiments conducted on a GC column with an i.d. of 0.32 mm, a GC flow rate of 0.6 mL/min is proposed for determining the D/H ratios of natural gas by GC/TC/IRMS. Although this value may be dependent on the instrument conditions used in this work, we believe that correct deltaD values of organic compounds with a few carbon atoms are obtained only when relatively low GC flow rates are used for D/H analysis by GC/TC/IRMS. Moreover, as the presence of trace water could significantly affect the determination of D/H ratios, a newly designed inlet liner was used to remove trace water contained in some gas samples.

Carbon isotope effects of DDTs in carrot during the digestion process using an in vitro test.

Compound-specific carbon isotope ratio analysis is a promising tool to assess the origins and fates of organic contaminants in many fields. The present study aims to investigate the isotope effects of dichloro-diphenyl-trichloroethane (DDT) and its degradates in carrots during digestion processes simulating the human gastrointestinal tract. To accurately interpret isotopic data obtained for unreleased DDTs (p,p-DDT, p,p-DDD and p,p-DDE) from carrots during digestion, spiked carrots with known delta(13)C values of DDTs were incubated in simulated gastric and intestinal solutions using a static in vitro model of the human gut. The delta(13)C values and concentrations of DDTs remaining in the carrot and in the digestive solutions were measured. The difference in the delta(13)C values of the added DDTs and the matrix-bound DDTs after digestion was always <0.50 per thousand, which is within the technical specification of the analytical system, although the released DDTs increased or decreased under the digestion conditions. The study demonstrated that there were no significant carbon isotopic fractionations during digestion. To our knowledge, this is the first report demonstrating the isotope effect of organic compounds during stomach and small intestine digestion, and the first reported isotope analyses of DDTs.

Improvement of 2,4-dinitrophenylhydrazine derivatization method for carbon isotope analysis of atmospheric acetone.

Through simulation experiments of atmospheric sampling, a method via 2,4-dinitrophenylhydrazine (DNPH) derivatization was developed to measure the carbon isotopic composition of atmospheric acetone. Using acetone and a DNPH reagent of known carbon isotopic compositions, the simulation experiments were performed to show that no carbon isotope fractionation occurred during the processes: the differences between the predicted and measured data of acetone-DNPH derivatives were all less than 0.5 per thousand. The results permitted the calculation of the carbon isotopic compositions of atmospheric acetone using a mass balance equation. In this method, the atmospheric acetone was collected by a DNPH-coated silica cartridge, washed out as acetone-DNPH derivatives, and then analyzed by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Using this method, the first available delta13C data of atmospheric acetone are presented.