Characterisation of the Dynamics of Leachate Contamination Plumes in the Surrounding of the Hulene - B Waste Dump, Maputo, Mozambique

The contamination of areas around solid urban waste dumps is a global challenge for the maintenance of environmental quality in large urban centres in developing countries. This study applied geophysical methods (electrical resistivity) to identify leachate contamina-tion plumes in the subsoil and groundwater, as well as to describe their temporal (2020 and 2021) dynamics in the lithology and groundwater around the Hulene - B waste dump, Maputo, Mozambique. Geophysical methods (electrical resistivity) were applied to identify possible groundwater contamination plumes, their dynamics, mechanisms of their enrichment and dispersion. Eight 400 m electrical resistivity profiles were performed, four profiles in January 2020 and four profiles in May 2021, overlapped, and the data were inverted with RES2D software. The electrical resistivity models indicate an E - W move-ment of large contamination plumes that dilute superficially into the natural surface wa-ter receiving basin and groundwater, creating zones of resistive anomalies. The thickness of the plumes in the subsurface environment was shown to be extensive in summer for profiles 1a and 2b and we associate it with the higher leachate production and migration mechanisms, which are intense in the hot and rainy season. Profile 4b showed the prop-agation of anomalous surface and subsurface areas, which was associated with higher leachate production and migration process in the new deposition zone (west). The spatial distribution of contamination plumes at both stations reduced significantly as we moved further away from the waste deposit, revealing the attenuating effect of groundwater and lithological substrate (Profile 3 a, b, and fig.7).

Sorption of Monothioarsenate to the Natural Sediments and Its Competition with Arsenite and Arsenate

Monothioarsenate (MTAsV) is one of the major arsenic species in sulfur- or iron-rich groundwater, and the sediment adsorption of MTAsV plays an important role in arsenic cycling in the subsurface environment. In this study, batch experiments and characterization are conducted to investigate the sorption characteristic and mechanism of MTAsV on natural sediments and the influences of arsenite and arsenate. Results show that MTAsV adsorption on natural sediments is similar to arsenate and arsenite, manifested by a rapid early increasing stage, a slowly increasing stage at an intermediate time until 8 h, before finally approaching an asymptote. The sediment sorption for MTAsV mainly occurs on localized sites with high contents of Fe and Al, where MTAsV forms a monolayer on the surface of natural sediments via a chemisorption mechanism and meanwhile the adsorbed MTAsV mainly transforms into other As species, such as AlAs, Al-As-O, and Fe-As-O compounds. At low concentration, MTAsV sorption isotherm by natural sediments becomes the Freundlich isotherm model, while at high concentration of MTAsV, its sorption isotherm becomes the Langmuir isotherm model. The best-fitted maximum adsorption capacity for MTAsV adsorption is about 362.22 μg/g. Furthermore, there is a competitive effect between MTAsV and arsenate adsorption, and MTAsV and arsenite adsorption on natural sediments. More specifically, the presence of arsenite greatly decreases MTAsV sorption, while the presence of MTAsV causes a certain degree of reduction of arsenite adsorption on the sediments before 4 h, and this effect becomes weaker when approaching the equilibrium state. The presence of arsenate greatly decreases MTAsV sorption and the presence of MTAsV also greatly decreases arsenate sorption. These competitive effects may greatly affect MTAsV transport in groundwater systems and need more attention in the future.

Diagenetic Controls on the Formation of the Anarraaq Clastic-Dominated Zn-Pb-Ag Deposit, Red Dog District, Alaska

The Anarraaq clastic-dominated (CD) Zn-Pb-Ag deposit (Red Dog district, Alaska, USA) has an inferred mineral resource of 19.4 Mt at 14.4% Zn, 4.2% Pb, and 73 g/t Ag and is spatially associated with a separate ~1 Gt barite body. This study presents new cross sections and petrographic evidence from the Anarraaq area. The barite body, previously shown to have formed in a shallow subsurface environment akin to a methane cold seep, contains multiple generations of barite with locally abundant calcite masses, which are discordant to sedimentary laminae, and is underlain by an interval of massive pyrite containing abundant framboids and radiolarians. Calcite and pyrite are interpreted to have formed by methane-driven diagenetic alteration of host sediment at the sulfate-methane transition (SMT). The sulfide deposit contains two zones of Zn-Pb mineralization bounded by faults of unknown displacement. The dominant hydrothermal minerals are marcasite, pyrite, sphalerite, quartz, and galena. The presence of hydrothermal pseudomorphs after barite, early pyrite resembling diagenetic pyrite associated with the barite body, and hydrothermal quartz and sphalerite filling voids formed by dissolution of carbonate all suggest that host sediment composition and origin was similar to that of the barite body prior to hydrothermal mineralization. Rhenium-osmium isochron ages of Ikalukrok mudstone (339.1 ± 8.3 Ma), diagenetic pyrite (333.0 ± 7.4 Ma), and hydrothermal pyrite (334.4 ± 5.3 Ma) at Anarraaq are all within uncertainty of one another and of an existing isochron age (~338 Ma) for the Main deposit in the Red Dog district. This indicates that the Anarraaq deposit formed soon after sedimentation and that hydrothermal activity was approximately synchronous in the district. The initial Os composition of the Anarraaq isochrons (0.375 ± 0.019–0.432 ± 0.025) is consistent with contemporaneous seawater, indicating that a mantle source was not involved in the hydrothermal system. This study highlights the underappreciated but important role of early, methane-driven diagenetic processes in the paragenesis of some CD deposits and has important implications for mineral exploration.

A density functional theory study of Fe(II)/Fe(III) distribution in single layer green rust: a cluster approach

Green rust (GR) is a potentially important compound for the reduction of heavy metal and organic pollutants in subsurface environment because of its high Fe(II) content, but many details of the actual reaction mechanism are lacking. The reductive capacity distribution within GR is a key to understand how and where the redox reaction occurs and computational chemistry can provide more details about the electronic properties of green rust. We constructed three sizes of cluster models of single layer GR (i.e., without interlayer molecules or ions) and calculated the charge distribution of these structures using density functional theory. We found that the Fe(II) and Fe(III) are distributed unevenly in the single layer GR. Within a certain range of Fe(II)/Fe(III) ratios, the outer iron atoms behave more like Fe(III) and the inner iron atoms behave more like Fe(II). These findings indicate that the interior of GR is more reductive than the outer parts and will provide new information to understand the GR redox interactions.

The Sources of Organic Carbon in the Deepest Ocean: Implication From Bacterial Membrane Lipids in the Mariana Trench Zone

Hadal trenches have higher microbial carbon turnover rates as compared to adjacent abyssal plains. However, the source of organic carbon in the trench remains enigmatic. In this study, we show that a fraction of organic carbon is possibly derived in situ and correlated with chemoautotrophic communities supported by the fluid discharge of water-rock interaction in the trench wall, based on analysis of glycerol dialkyl glycerol tetraether (GDGT) membrane lipids, including archaeal isoprenoid GDGTs (IsoGDGTs) and bacterial branched GDGTs (BrGDGTs), in sediments and rocks of the Mariana and Yap Trenches, northwest Pacific Ocean. These trench sediments contained relative higher BrGDGTs ratios, which was a rare observation in the open ocean. The BrGDGT-to-IsoGDGT ratios ranged in 0.02–0.88 (mean = 0.10 ± 0.11) in sediments and 0.09–0.38 (mean = 0.17 ± 0.13) in altered rocks. The calculated values of branched and isoprenoid tetraether (BIT) index ranged from 0.02–0.73 (mean = 0.18 ± 0.11) in sediments and from 0.16–0.9 in altered rocks (mean = 0.37 ± 0.27). Moreover, these GDGTs exhibited similar characteristics to those of altered basalt rocks, indicating inputs of organic carbon from the trench subsurface environment. Thus, in addition to organic-rich material settling, we propose chemoautotrophic activity in oceanic crust could be an additional source of organic carbon in the deepest part of the ocean, with an important role in deep-sea carbon cycles.

Terrestrial hydroclimatic variability in basins of Southern Siberia driven by different states of permafrost degradation

<p>Changes in the cryosphere caused by global warming are expected to alter the hydrologic system, with inevitable consequences for freshwater availability to humans and ecosystems. Quantitative understandings of the historical hydrologic changes in response to permafrost degradation is essential for projecting future changes with respect to the continuing and possibly intensifying warming. Here we investigate past hydro-climatic changes over three southern Siberian basins with diverse permafrost properties: in the Selenga catchment, all three permafrost types occur, i.e., discontinuous, sporadic and isolated permafrost; the Lena Basin (at gauge Tabaga) is mostly underlain by discontinuous permafrost, while the Aldan is dominated by continuous permafrost.</p><p>Based on the reconstruction of terrestrial water storage changes (TWS) from the GRACE satellite mission and hydro-climatic time series over the period 1984-2013, our results show very different change patterns in the TWS among these three basins. There is an unprecedented reduction of TWS (-9.8 km<sup>3</sup>) in the Selenga basin, but remarkable increases (14.4 km<sup>3</sup> and 13.1 km<sup>3</sup>) in the Lena-Tabaga and Aldan basins, respectively. The diverse changes in TWS, runoff and precipitation over each basin suggest different hydrologic response mechanisms to permafrost degradation under a warming climate. The Selenga, dominated by lateral degradation (i.e., decreasing permafrost extent), suffers severe water loss via deep infiltration of water that was previously stored close to the surface, which induces a drier surface and subsurface drainage system. In contrast, in the Aldan basin, determined by vertical degradation, thicker active layers develop which sustain a water-rich surface and subsurface environment. In the Lena-Tabaga basin finally, which is characterized by both lateral and vertical degradations, the further development of lateral degradation has led to a stronger increase in groundwater storage in comparison to surface runoff during the increased precipitation states, suggesting a potentially groundwater-dominated hydrologic system in this basin. Our findings are of great importance for the regional water management in permafrost-affected regions under ongoing warming.</p>