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Porewater arsenic mobility above the groundwater table has been recognized as a potential cause of arsenic-rich groundwater, but the processing pathways of dissolved organic matter (DOM) in that hyporheic zone and their effect on porewater arsenic release remain poorly understood. To address these issues, two porewater profiles were sampled in a surface water-groundwater interaction zone from the Hetao Basin, China, to monitor the porewater geochemistry and DOM molecular characteristics. The results show that the porewater arsenic, Fe(II), and DOC concentrations were all significantly higher than those of the intruding pond water, and were located above the conservative mixing model lines. This indicates a net release of these solutes from the sediment. By comparing the porewater with pond water DOM, we found that the carboxyl-rich alicyclic molecules (CRAM) were selectively preserved, carbohydrates and aliphatics/proteins were preferentially consumed, and low O/C-ratio compounds with high bioproduction index (I_bioprod) and terrestrial index (I_terr) were produced. The transformation of CHO to CHOS compounds also represented a pathway of recalcitrant DOM production. The produced recalcitrant organic compounds mostly contributed to the elevated porewater DOC concentrations, but their contribution decreased along the filtration path. The consumption of labile DOM compounds would be responsible for Fe(III) hydroxide reduction and arsenic release. The generated recalcitrant DOM may also be a driver of porewater arsenic mobility by acting as electron shuttles. This study highlights the importance of the hyporheic zone in shaping shallow groundwater DOM composition and the potential contribution to arsenic enrichment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The concentrations, composition patterns, transport and fate of PAHs in semi-arid and arid soils such as in Central Asia are not well known. Such knowledge is required to manage the risk posed by these toxic chemicals to humans and ecosystems in these regions. To fill this knowledge gap, we determined the concentrations of 21 parent PAHs, 4,5-methylenephenanthrene, 6 alkylated PAHs, and biphenyl in soils from 11 sampling locations (0-10, 10-20 cm soil depths) along a 20-km transect downwind from the Almalyk metal mining and metallurgical industrial complex (Almalyk MMC), Uzbekistan. The concentrations of Σ29 PAHs and Σ16 US-EPA PAHs were 41-2670 ng g -1 and 29-1940 ng g -1 , respectively. The highest concentration of Σ29 PAHs occurred in the immediate vicinity of the copper smelting factory of the Almalyk MMC. The concentrations in topsoil decreased substantially to a value of ≤ 200 ng g -1 (considered as background concentration) at ≥ 2 km away from the factory. Low molecular weight PAHs dominated the PAH mixtures at less contaminated sites and high molecular weight PAHs at the most contaminated site. The concentration of Σ16 US-EPA PAHs did not exceed the precautionary values set by the soil quality guidelines of, e.g., Switzerland and Germany. Similarly, the benzo[a]pyrene equivalent concentration in soils near the Almalyk MMC did not exceed the value set by the Canadian guidelines for the protection of humans from carcinogenic PAHs in soils. Consequently, the cancer risk due to exposure to PAHs in these soils can be considered as low., (© 2021. The Author(s).)