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Substantial halogenated organic chemicals stored in permafrost soils on the Tibetan Plateau

Nature Geoscience volume 16, pages 989–996 (2023)Cite this article

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Abstract

Permafrost in the polar regions potentially stores large amounts of toxic chemicals, including organic compounds bound with halogens. The release of such halogenated organic chemicals (HOC) from thawing permafrost represents a potential global concern with climate change. However, the exact inventory of HOC remains uncertain because conventional analytical techniques largely overlook nonextractable residues. Here we present an inventory of HOC in permafrost soils sampled from the Tibetan Plateau using stepwise chemical treatment following conventional solvent extraction to release and analyse the nonextractable residues. We identify more than 270 types of HOC, with total mean concentration of 310,000 ng g−1, of which 180,000 ng g−1 are naturally sourced based on their molecular structures. We also find unexpectedly high fractions of the nonextractable residues, contributing more than 99% of the total HOC, much higher than those reported for other soils and sediments. Up to 85% of the nonextractable residues are physically entrapped in soils rather than chemically bound, such that they could readily be remobilized if soil properties change. We suggest that this substantial stock of HOC in Tibetan Plateau permafrost poses potentially important future risks to local ecosystems in a warming climate.

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Fig. 1: Workflow of solvent extraction and stepwise chemical treatment.
Fig. 2: Chromatographic and identified results of HOC.
Fig. 3: Quantified results of HOC.
Fig. 4: Results of this work versus literature data.
Fig. 5: Distribution of HOC as EF and NER.
Fig. 6: Opposite distribution of HOC in the Tibetan Plateau permafrost and in industrially contaminated soils.

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Data availability

All data within the paper and its Supplementary Information files are available through Figshare at https://doi.org/10.6084/m9.figshare.24087459. Source data are provided with this paper.

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Acknowledgements

This work was supported by the Natural Science Foundation of China (42107390, to X.Z.), Gansu Provincial Key Lab Research Open Project Fund (SZDKFJJ20201204, to X.Z.) from the Northwest Institute of Eco-Environment and Resources, the Second Tibetan Plateau Scientific Expedition and Research (STEP) programme (2019QZKK0605, to Xiaoping Wang), the NSFC–Horizon joint programme (31861133003, to R.J.) and the Alliance of International Science Organizations (ANSO-CR-KP-2021-05, to G.Z.). China Scholarship Council sponsored X.Z.’s earlier doctoral study and research in Germany to collect the urban soil data. SEP Analytical Shanghai Co Ltd provided instrumental support for selected samples. The initiation of this study was supported by Fudan University’s internal grants to Z.W.

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Authors and Affiliations

  1. Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science and Engineering, Fudan University, Shanghai, China

    Xiaojing Zhu, Fan Yang, Zhen Li, Mingliang Fang, Xiaofei Wang, Xingnan Ye, Yingjun Chen, Lin Wang, Jianmin Chen & Zimeng Wang

  2. Gansu Province Key Laboratory of Petroleum Resources, China Northwest Institute of Eco-Environment and Resources, Chinese Academy of Sciences, Lanzhou, China

    Suping Ma & Ting Zhang

  3. State Key Laboratory of Tibetan Plateau Earth System, Resources and Environment (TPESRE), Institute of Tibetan Plateau Research, Chinese Academy of Sciences, Beijing, China

    Cunlin Li & Xiaoping Wang

  4. University of Chinese Academy of Sciences, Beijing, China

    Cunlin Li, Xiaoping Wang & Gan Zhang

  5. School of Earth Resources, China University of Geosciences, Wuhan, China

    Qiulei Guo

  6. State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, China

    Gan Zhang

  7. State Key Laboratory of Pollution Control and Resource Reuse, School of Environment, Nanjing University, Nanjing, China

    Rong Ji

  8. Institute for Environmental Research, RWTH Aachen University, Aachen, Germany

    Andreas Schäffer

  9. National Observations and Research Station for Wetland Ecosystems of the Yangtze Estuary, Institute of Eco-Chongming, Fudan University, Shanghai, China

    Lin Wang, Jianmin Chen & Zimeng Wang

  10. Shanghai Institute of Pollution Control and Ecological Security, Shanghai, China

    Lin Wang & Zimeng Wang

  11. Ministry of Education Key Laboratory of Polar Atmosphere-Ocean-Ice System for Weather and Climate, IRDR International Center of Excellence on Risk Interconnectivity and Governance on Weather/Climate Extremes Impact and Public Health, Institute of Atmospheric Sciences, Fudan University, Shanghai, China

    Jianmin Chen

  12. Stockbridge School of Agriculture, University of Massachusetts, Amherst, MA, USA

    Baoshan Xing

  13. Institute of Geology and Geochemistry of Petroleum and Coal, RWTH Aachen University, Aachen, Germany

    Jan Schwarzbauer

Authors
  1. Xiaojing Zhu
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  2. Fan Yang
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  20. Jan Schwarzbauer
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Contributions

Conceptualization was carried out by X.Z., Z.W. and J.S. Methodology was carried out by J.S., X.Z., A.S., R.J., G.Z. and M.F. Investigation was carried out by X.Z., Q.G., F.Y., Z.L., Xiaoping Wang, Xiaofei Wang, Y.C., X.Y., L.W., J.C. and B.X. Sampling was carried out by S.M., T.Z., C.L. and X.Z. Visualization was carried out by X.Z. and F.Y. Writing was carried out by X.Z., M.F., Z.W. and J.S. All authors reviewed and edited the manuscript.

Corresponding authors

Correspondence to Zimeng Wang or Jan Schwarzbauer.

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Nature Geoscience thanks Hans Richnow and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Xujia Jiang, in collaboration with the Nature Geoscience team.

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Extended data

Extended Data Fig. 1 Location and quantified HOC results of each permafrost sample.

(a) Sampling sites of this work. See Supplementary Table 1 for further information on the samples. Permafrost zonation data from refs. 63,64. (b) The HOC (halogenated organic chemicals) levels as EF (extractable fraction) and NER (nonextractable residues) in the surface permafrost soils. (c) Vertical distribution of five HOC groups as EF and NER.

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Extended Data Fig. 2 Illustration of HOC molecules detected in this work.

HOC (halogenated organic chemicals) molecules detected (a) in the Tibetan Plateau permafrost soils and (b) in Bitterfelfd-Wolfen soils. Note that each HOC molecular structure is an exemplifying one out of its other isomers (if at all). EF, extractable fraction; NER, nonextractable residues. The suspected moieties obtained by different bond cleavage indicate that these NER-HOC are possible to be previously bound with soil organic matter via covalent bonds because different chemical treatment steps cleave different target bonds and release HOC containing the corresponding functional groups (to be specific, ester/amide bond-cleavage results in hydroxyl, amine, and carboxyl; ether bond-cleavage results in hydroxyl and bromine substitution; unsaturated C-C bound-cleavage results in carbonyl). Note that this is applicable only when NER-HOC is detected in the corresponding chemical treatment step.

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Extended Data Fig. 3 Distribution and incorporating ways of HOC.

(a) Distribution and incorporating ways of five HOC (halogenated organic chemicals) groups in the surface samples of the Tibetan Plateau permafrost (the left panel, the data are arithmetic means for the pie charts (n = 23), in the subsurface samples (10–60 cm depth) of the Tibetan Plateau permafrost (the middle panel, the data are arithmetic means for each pie chart (n = 10, two profiles, five depths each)), and in the surface soils from the industrial megasite Bitterfeld-Wolfen (the right panel, the data are arithmetic means for each pie chart (n = 2). EF, extractable fraction; NER, nonextractable residues. (b) Our hypothetical ways of different groups of NER-HOC (nonextractable HOC) incorporating into soil substances based on the results of the surface samples of the Tibetan Plateau permafrost. The moieties of each covalently bound NER-HOC and the associated soil organic matter (SOM) macromolecules are colored in pink and blue, respectively. Note that the illustrated molecules are random exemplifying HOC of each group.

Source data

Extended Data Fig. 4 Pearson correlation analysis.

(a) Pearson correlation analysis of HOC (halogenated organic chemicals) molecular descriptors to their log (EF/NER) (logarithm of 10), (EF, extractable fraction; NER, nonextractable residues). (b) Pearson correlation analysis of sample properties (total organic carbon (TOC) content and the sampling location topography) to HOC concentrations and log (EF/NER). Smaller distances of sampling sites from Mt Zuoqiupu, Mt Everest, and Mt Muztagata indicate higher impacts of tropical monsoon, Indian monsoon, and westerly wind, respectively. No mathematical correction was made for multiple comparisons. p-values (two-tailed) are illustrated in the upper triangular of each panel. A significant mark (*) is labelled when the p-value is lower than 0.05 (threshold of significance).

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Extended Data Fig. 5 Risk levels of Tibetan HOC.

Induced environmental risk of HOC (halogenated organic chemicals) by NER (nonextractable residues) data in the Tibetan Plateau permafrost. The HOC with no blue dot are those with no detection in their EF (extractable fraction). The soil screening levels of both compounds are collected from US EPA Regional Screening Levels (RSLs) - Generic Tables (target cancer risk = 1E-06, hazard quotients = 0.1, U.S. EPA, https://www.epa.gov/risk/regional-screening-levels-rsls-generic-tables).

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Extended Data Fig. 6 Vertical distribution of HOC.

(a) Vertical distribution of five HOC (halogenated organic chemicals) groups with different origins in two soil profiles (S6 profile and S7 profile) from the Tibetan Plateau. (b) Percentage distribution of different sourced HOC as EF (extractable fraction) and as NER (nonextractable residues) at various depths in two soil profiles (S6 profile and S7 profile) from the Tibetan Plateau. (c) Vertical distribution of three pesticide HOC (insecticide HCH (hexachlorocyclohexane), antimicrobial trichloropyridinamine, herbicide simazine) in the two Tibetan permafrost.

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Extended Data Fig. 7 Distribution of HOC and different organic halogens in surface soils.

(a) and (b) are the distribution of each HOC (as EF (extractable fraction), covalently bound NER (nonextractable residues), and physically bound NER) in five groups of the HOC categories in the surface soils from Tibetan Plateau and Bitterfeld-Wolfen, respectively. Boxplots show the median (the horizontal lines), the first to third quartiles (the lower and upper hinges), and the 1.5×interquartile ranges (whiskers). The integrated pathways and amounts of the degradation products of some well-known HOC (halogenated organic chemicals) commonly detected in the surface soils from (c) the Tibetan Plateau (n = 23) and (d) Bitterfeld-Wolfen (n = 2). The pathways are adapted from Schwarzbauer and Jovančićević (2018); Ricking and Schwarzbauer (2008); Scheunert (1994); Middeldorp et al. (1996); Quintero (2005); Parlar and Angerhöfer (1995)19,78,79,80,81,82. (e) Distribution of organic halogens in the surface soils from the Tibetan Plateau (arithmetic means, n = 23) and Bitterfeld-Wolfen (arithmetic means, n = 2). Each organic halogen content was calculated by multiplying the concentrations of the corresponding HOC (EF + NER) respectively by their halogen mass to molecular weight ratios. Note that the calculated total organic halogen content does not necessarily agree with the soil organic halogen content, as our method cannot guarantee complete separation of all soil organic matter.

Source data

Extended Data Fig. 8 NER assignment and comparison of HOC from the two sites.

(a) NER (nonextractable residues) categorization scheme, as highly possible covalently bound NER, potential covalently bound NER, and affirmatory physically entrapped NER. Note that organobromines detected solely after BBr3 treatment are pre-excluded from the HOC screening list before categorization. (b) Half violin plot showing the number of HOC (halogenated organic chemicals) detected in two randomly selected samples in our Tibetan Plateau surface soil sample set, n = 253. (c) Distribution of EF (extractable fraction), highly possible covalently bound NER, potential covalently bound NER, and affirmatory physically entrapped NER for all HOC and the five HOC groups in samples from the Tibetan Plateau (surface samples, n = 23; subsurface samples, n = 10) and from Bitterfeld- Wolfen (surface samples, n = 2).

Source data

Extended Data Fig. 9 Remobilization of HOC from the Permafrost samples.

(a) Changes of the concentrations of EF-HOC (extractable halogenated organic chemicals) in incubated soils (S15, S18, and Sterilized S18) under slightly increased temperature conditions (mean ± s.d., n = 3). (b) Remobilization levels of previous covalently bound (the upper panel) and physically entrapped (the lower panel) NER-HOC (nonextractable HOC) (mean ± s.d., n = 3, the error bars represent the s.d. of sum of the five HOC groups).

Source data

Extended Data Fig. 10 Comparison of EF-HOC (extractable halogenated organic chemicals) levels in global and Tibetan Plateau soils.

Literature hexachlorocyclohexane (HCH) (a) and hexachlorobenzene (HCB) (b) EF levels in global soils (the left panels) and in Tibetan Plateau soils (the right panels)4,13,14,52,53,54,55,56,57,58,59,62,83,84,85,86,87,88,89,90,91,92,93,94,95,96,97,98,99,100,101,102,103,104,105,106,107,108,109,110,111,112,113,114,115,116,117,118,119,120,121,122,123,124,125,126,127,128,129,130,131,132,133,134,135,136,137,138,139,140,141,142,143,144,145,146,147,148,149,150,151,152,153,154,155,156,157,158,159,160,161,162,163,164. Note that the literature data with no detection of either compounds or below their detection limits are not illustrated.

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Supplementary information

Supplementary Information

Supplementary Tables 1, 4 and 6, and legends for separate Supplementary Tables 2, 3 and 5.

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Zhu, X., Yang, F., Li, Z. et al. Substantial halogenated organic chemicals stored in permafrost soils on the Tibetan Plateau. Nat. Geosci. 16, 989–996 (2023). https://doi.org/10.1038/s41561-023-01293-1

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