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Geochemical and microbial characteristics of seepage water and mineral precipitates in a radwaste disposal facility impacted by seawater intrusion and high alkalinity

The construction of an underground facility can dramatically change the quality, flow direction, and level of groundwater. It may also impact subsurface microbial composition and activity. Groundwater quality was monitored over eight years in two observational wells near an underground disposal facility on the east coast of South Korea. The results showed dramatic increases in dissolved ions such as O 2 , Na, Ca, Mg, and SO 4 during facility construction. Seepage water samples downgradient from the silos and tunnels, and precipitates deposited along the seepage water flow path were collected to determine the impact inside the disposal facility. X-ray analysis (powder X-ray diffraction (pXRD) and X-ray absorption fine structure (XAFS)) were used to characterize the mineral precipitates. Microbial community composition was determined by 16S rRNA gene sequencing. The seepage water composition was of two types: Ca-Cl and Ca-Na-HCO 3 . The ratio of Cl and δ 18 O showed that the Ca-Cl type seepage water was influenced by groundwater mixed with seawater ranging from 2.7% to 15.1%. Various sulfate-reducing bacteria were identified in the Ca-Cl type seepage water, exhibiting relatively high sulfate content from seawater intrusion. Samples from the Ca-Na-HCO 3 type seepage water had an extremely high pH (>10) and abundance of Hydrogenophaga. The precipitates observed along the flow path of the seepage water included calcite, ferrihydrite, green rust, and siderite, depending on seepage water chemistry and microbial activity. This study suggests that the construction of underground structures creates distinct, localized geochemical conditions (e.g., high alkalinity, high salinity, and oxic conditions), which may impact microbial communities. These biogeochemical changes may have undesirable large-scale impacts such as water pump clogging. Overall, an understanding of the process and long-term monitoring are essential to assess the safety of underground facilities.

54 ENVIRONMENTAL SCIENCES↗

Materials Data on CaCl2 by Materials Project

CaCl2 is Rutile structured and crystallizes in the tetragonal P4_2/mnm space group. The structure is three-dimensional. Ca2+ is bonded to six equivalent Cl1- atoms to form a mixture of corner and edge-sharing CaCl6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are four shorter (2.76 Å) and two longer (2.77 Å) Ca–Cl bond lengths. Cl1- is bonded in a distorted trigonal planar geometry to three equivalent Ca2+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on CaCl2 by Materials Project

CaCl2 is Hydrophilite structured and crystallizes in the orthorhombic Pnnm space group. The structure is three-dimensional. Ca2+ is bonded to six equivalent Cl1- atoms to form a mixture of edge and corner-sharing CaCl6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are four shorter (2.76 Å) and two longer (2.77 Å) Ca–Cl bond lengths. Cl1- is bonded in a distorted trigonal planar geometry to three equivalent Ca2+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on CaCl2 by Materials Project

CaCl2 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Ca2+ is bonded to five Cl1- atoms to form a mixture of distorted edge and corner-sharing CaCl5 trigonal bipyramids. There are a spread of Ca–Cl bond distances ranging from 2.61–2.80 Å. There are two inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a distorted trigonal non-coplanar geometry to three equivalent Ca2+ atoms. In the second Cl1- site, Cl1- is bonded in a distorted bent 150 degrees geometry to two equivalent Ca2+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on CaCl2 by Materials Project

CaCl2 is Hydrophilite-like structured and crystallizes in the orthorhombic Pbcn space group. The structure is three-dimensional. Ca2+ is bonded to six equivalent Cl1- atoms to form a mixture of edge and corner-sharing CaCl6 octahedra. The corner-sharing octahedra tilt angles range from 52–53°. There are four shorter (2.76 Å) and two longer (2.79 Å) Ca–Cl bond lengths. Cl1- is bonded in a distorted trigonal planar geometry to three equivalent Ca2+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on CaCl2 by Materials Project

CaCl2 is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Ca2+ is bonded in a body-centered cubic geometry to eight equivalent Cl1- atoms. All Ca–Cl bond lengths are 2.92 Å. Cl1- is bonded to four equivalent Ca2+ atoms to form a mixture of edge and corner-sharing ClCa4 tetrahedra.

36 MATERIALS SCIENCE↗