Hydrochemistry of urban groundwater, Seoul, Korea: the impact of subway tunnels on groundwater quality

Hydrogeologic and hydrochemical data for subway tunnel seepage waters in Seoul (Republic of Korea) were examined to understand the effect of underground tunnels on the degradation of urban groundwater. A very large quantity of groundwater (up to 63 million m³ year^− 1) is discharged into subway tunnels with a total length of 287 km, resulting in a significant drop of the local groundwater table and the abandonment of groundwater wells. For the tunnel seepage water samples (n = 72) collected from 43 subway stations, at least one parameter among pathogenic microbes (total coliform, heterotrophic bacteria), dissolved Mn and Fe, NH₄⁺, NO₃⁻, turbidity, and color exceeded the Korean Drinking Water Standards. Locally, tunnel seepage water was enriched in dissolved Mn (avg. 0.70 mg L^− 1, max. 5.58 mg L^− 1), in addition to dissolved Fe, NH₄⁺, and pathogenic microbes, likely due to significant inflow of sewage water from broken or leaking sewer pipes.Geochemical modeling of redox reactions was conducted to simulate the characteristic hydrochemistry of subway tunnel seepage. The results show that variations in the reducing conditions occur in urban groundwater, dependent upon the amount of organic matter-rich municipal sewage contaminating the aquifer. The organic matter facilitates the reduction and dissolution of Mn- and Fe-bearing solids in aquifers and/or tunnel construction materials, resulting in the successive increase of dissolved Mn and Fe. The present study clearly demonstrates that locally significant deterioration of urban groundwater is caused by a series of interlinked hydrogeologic and hydrochemical changes induced by underground tunnels.     

Geochemistry of a septic-system plume in a coastal barrier bar, Point Pelee, Ontario, Canada

The major ion and trace metal geochemistry of a septic system plume in a shallow sand aquifer was characterized to assess geochemical processes controlling the transport of nutrients and their release to a nearby wetland. The plume was generated from a 16-year-old tile bed, and is more than 60 m long, 40 m wide and 7 m thick. The groundwater pH at the site is near neutral, but up to 0.4 units lower in the plume core as a result of H⁺ generated from NH₃ and DOC oxidation in the unsaturated zone. The plume can be divided into distinct redox zones, which show differences in nutrient mobility. Proximal to the tile bed, there is a shallow suboxic zone, with intermediate Eh values (>400 mV), low concentrations of dissolved oxygen (<1.0 mg/l), and elevated concentrations of Mn (1–3 mg/l) and nutrients (10–80 mg/l NO₃–N, 1–15 mg/l NH₃–N, 0.1–1.5 mg/l PO₄–P, 6–13 mg/l dissolved organic carbon). At the base of the aquifer, there is a reduced zone (Eh<200 mV) with elevated concentrations of Fe (1–14 mg/l), PO₄ and NH₃, but negligible concentrations of NO₃ (<0.01 mg/l N). Distal from the tile bed, the shallow groundwater is suboxic to oxic, and has elevated concentrations of NO₃ and NH_3, but negligible PO₄. In the lower reduced zone, elevated concentrations of PO₄ occur up to 60 m away. The release of groundwater containing even very low concentrations of PO₄ (<0.02 mg/l P) can lead to the development of eutrophic conditions in surface water bodies. Geochemical calculations indicate that, in the Mn-rich zone, the groundwater is close to saturation or supersaturated with respect to hydroxyapatite, rhodochrosite, calcite and ferrihydrite. In the reduced zone, the groundwater is close to saturation or supersaturated with respect to hydroxyapatite, vivianite, calcite and siderite. Formation of these phases, or related phases, are likely limiting the concentrations of dissolved PO₄, Fe and Mn and controlling the geochemical evolution of the plume.     

Hydrogeological and biogeochemical constrains of arsenic mobilization in shallow aquifers from the Hetao basin, Inner Mongolia

Little is known about the importance of drainage/irrigation channels and biogeochemical processes in arsenic distribution of shallow groundwaters from the Hetao basin. This investigation shows that although As concentrations are primarily dependent on reducing conditions, evaporation increases As concentration in the centre of palaeo-lake sedimentation. Near drainage channels, groundwater As concentrations are the lowest in suboxic-weakly reducing conditions. Results demonstrate that both drainage and irrigation channels produce oxygen-rich water that recharges shallow groundwaters and therefore immobilize As. Groundwater As concentration increases with a progressive decrease in redox potential along the flow path in an alluvial fan. A negative correlation between SO₄²⁻ concentrations and δ³⁴S values indicates that bacterial reduction of SO₄²⁻ occurs in reducing aquifers. Due to high concentrations of Fe (>0.5 mg L⁻¹), reductive dissolution of Fe oxides is believed to cause As release from aquifer sediments. Target aquifers for safe drinking water resources are available in alluvial fans and near irrigation channels.     

Development of steady-state phosphate concentrations in septic system plumes

Long-term monitoring of PO₄⁻³ behaviour in a well-defined septic system plume on calcareous sand (Cambridge site) shows that, after 17 yr of system operation, a distinct PO₄⁻³ plume (PO₄⁻³−P > 1 mg L⁻¹) is present extending 20 m downgradient from the infiltration bed. The PO₄³⁻ plume migration velocity is 1 m yr⁻¹, reflecting retardation by a factor of 20 compared to the groundwater velocity. During monitoring between years 10 to 17, an expanding steady-state zone was noted below the infiltration bed where PO₄³⁻ −P levels remained consistently near 4 mg L⁻¹, a value 25% lower than the average effluent value (6.3 mg L⁻¹). The pattern of attenuation — a 25% mass loss in the 2-m-thick vadose zone, then little further attenuation along the flowpath — is suggestive of a condition of equilibrium with a controlling phosphate mineral phase. Chemical equilibrium modelling shows supersaturation with respect to hydroxylapatite and variscite. Four other field sites are identified from the literature and from our work where similar steady-state PO₄³⁻ zones are present in septic system plumes. In these, steady-state levels range from 15% to 68% of effluent values, with lower concentrations observed in the more acidic plumes, again indicative of a mineral solubility control, possibly variscite.PO₄³⁻ behaviour in these plumes suggests that, although P migration velocity is controlled by the processes of sorption, the magnitude of PO₄³⁻ that is present is governed by the constraints of phosphate mineral solubility. When septic systems on sands are located relatively close to sensitive surface water bodies and when long-term downgradient impact is the primary concern, more attention should be focused on the geochemical conditions that control PO₄³⁻ mineral solubility rather than only on the sorption characteristics of the sediment.     

Distribution and variability of redox zones controlling spatial variability of arsenic in the Mississippi River Valley alluvial aquifer, southeastern Arkansas

Twenty one of 118 irrigation water wells in the shallow (25-30 m thick) Mississippi River Valley alluvial aquifer in the Bayou Bartholomew watershed, southeastern Arkansas had arsenic (As) concentrations (<0.5 to 77 microg/L) exceeding 10 microg/L. Sediment and groundwater samples were collected and analyzed from the sites of the highest, median, and lowest concentrations of As in groundwater in the alluvial aquifers located at Jefferson County, Arkansas. A traditional five-step sequential extraction was performed to differentiate the exchangeable, carbonate, amorphous Fe and Mn oxide, organic, and hot HNO(3)-leachable fraction of As and other compounds in sediments. The Chao reagent (0.25 M hydroxylamine hydrochloride in 0.25 M HCl) removes amorphous Fe and Mn oxides and oxyhydroxides (present as coatings on grains and amorphous minerals) by reductive dissolution and is a measure of reducible Fe and Mn in sediments. The hot HNO(3) extraction removes mostly crystalline metal oxides and all other labile forms of As. Significant total As (20%) is complexed with amorphous Fe and Mn oxides in sediments. Arsenic abundance is not significant in carbonates or organic matter. Significant (40-70 microg/kg) exchangeable As is only present at shallow depth (0-1 m below ground surface). Arsenic is positively correlated to Fe extracted by Chao reagent (r=0.83) and hot HNO(3) (r=0.85). Arsenic extracted by Chao reagent decreases significantly with depth as compared to As extracted by hot HNO(3). Fe (II)/Fe (the ratio of Fe concentration in the extracts of Chao reagent and hot HNO(3)) is positively correlated (r=0.76) to As extracted from Chao reagent. Although Fe (II)/Fe increases with depth, the relative abundance of reducible Fe decreases noticeably with depth. The amount of reducible Fe, as well as As complexed to amorphous Fe and Mn oxides and oxyhydroxides decreases with depth. Possible explanations for the decrease in reducible Fe and its complexed As with depth include historic flushing of As and Fe from hydrous ferric oxides (HFO) by microbially-mediated reductive dissolution and aging of HFO to crystalline phases. Hydrogeochemical data suggests that the groundwater in the area falls in the mildly reducing (suboxic) to relatively highly reducing (anoxic) zone, and points to reductive dissolution of HFO as the dominant As release mechanism. Spatial variability of gypsum solubility and simultaneous SO(4)(2-) reduction with co-precipitation of As and sulfide is an important limiting process controlling the concentration of As in groundwater in the area.     

Phosphorus characterization in sediments impacted by septic effluent at four sites in central Canada

Characterization of phosphorus (P) enriched solids was undertaken in the sediments below four mature septic system infiltration beds, where previous monitoring of phosphate (PO₄) concentrations in the groundwater had indicated that substantial retention of P was occurring in the vadose zone. At each site, zones of sediment P enrichment were identified by an acid extraction procedure. Acid extractable sediment P concentrations were found to be 2–5 times higher than background values, within narrow discrete zones generally 10–30 cm in thickness, located within one meter of the infiltration pipes. Back scattered electron images of the P enriched zones indicated that the P solids occurred as distinct authigenic grains (up to 300 μm diameter) and as grain coatings. Microprobe analyses indicated predominantly Fe–P in calcareous sediments (Cambridge and Langton) and Al–Fe–P in non-calcareous sediments (Muskoka and Harp Lake). Porewater analyses indicated that the zones of P accumulation were closely associated with zones of redox change characterized by the conversion of effluent NH₄⁺ to NO₃⁻. The data suggests that a substantial amount of the septic derived P is being attenuated by mineral precipitation reactions that occur rapidly after the effluent encounters subsurface sediments. Reductive dissolution of ferric (oxy)hydroxide minerals as a consequence of reducing environments near the infiltrations pipes, the release of Fe²⁺ in solution and subsequent conversion of Fe²⁺ to Fe³⁺ may promote the precipitation of ferric or ferrosoferric PO₄ minerals. In sediments with limited buffering capacity (calcite deficient), the decrease in pH resulting from effluent oxidation may cause Al (oxy)hydroxide dissolution and subsequent precipitation of Al–P rich phases. These precipitation reactions appear to have the capacity to immobilize a substantial amount of septic derived P (25–99% at these sites) for a considerable period of time.     

A detailed field-based evaluation of naphthenic acid mobility in groundwater

An anaerobic plume of process-affected groundwater was characterized in a shallow sand aquifer adjacent to an oil sands tailings impoundment. Based on biological oxygen demand measurements, the reductive capacity of the plume is considered minimal. Major dissolved components associated with the plume include HCO₃, Na, Cl, SO₄, and naphthenic acids (NAs). Quantitative and qualitative NA analyses were performed on groundwater samples to investigate NA fate and transport in the subsurface. Despite subsurface residence times exceeding 20 years, significant attenuation of NAs by biodegradation was not observed based on screening techniques developed at the time of the investigation. Relative to conservative tracers (i.e., Cl), overall NA attenuation in the subsurface is limited, which is consistent with batch sorption and microcosm studies performed by other authors. Insignificant biological oxygen demand and low concentrations of dissolved As (< 10 µg L^− 1) in the plume suggest that the potential for secondary trace metal release, specifically As, via reductive dissolution reactions driven by ingress of process-affected water is minimal. It is also possible that readily leachable As is not present in significant quantities within the sediments of the study area. Thus, for similar plumes of process-affected groundwater in shallow sand aquifers which may occur as oil sands mining expands, a reasonable expectation is for NA persistence, but minimal trace metal mobilization.     

Acute toxicity of arsenic to Aliivibrio fischeri (Microtox® bioassay) as influenced by potential competitive–protective agents

In this study, we investigated the effect of some potential alleviative compounds against the acute toxicity of arsenic (As^V, As^III and DMA^V) on Aliivibrio fischeri (formerly Vibrio fischeri), a bioluminescent model bacterium, through the Microtox® bioassay. The compounds studied differed in their mechanism of action, and they included the following: phosphate and glycerol, as chemical analogues (and potential competitors) of As^V or As^III, respectively; citrate, a weak natural organic ligand; and the antioxidant ascorbic acid. Special attention was paid to phosphate effects, a widespread pollutant in natural environments. As^V was found to be more acutely toxic than As^III to A. fischeri, in accordance with its higher interaction with the bacteria. Both As^V and As^III were found to be much more acutely toxic than DMA^V, which was essentially non-acutely toxic even at very high concentrations. Phosphate presence (at equimolar P/As ratios or higher) resulted in the almost total suppression of bioluminescence inhibition, suggesting it exerts an alleviative effect against As^V acute toxicity on A. fischeri. Interestingly, the uptake and the percentage of extracellular As^V were not affected by the addition of phosphate, suggesting that such protective effect does not result from the competition for their common transporters. In contrast, the acute toxicity of As^III was essentially unaffected by phosphate. Glycerol did not decrease the acute toxicity or the uptake of As^III by A. fischeri, denoting the likely occurrence of an additional mechanism for As^III uptake in such bacteria. Similarly, citrate and ascorbic acid essentially did not caused alleviation of As^V or As^III acute toxicity. As for environmental and operational implications, P could beneficially protect aquatic microorganisms against acute detrimental effects of As^V, whilst its presence could mask the toxicity due to As^V when assessed using the Microtox® bioassay, thus leading to seriously underestimate the actual ecological and health risks.     

Mobilization of arsenic in aquifers from the Datong Basin,China: Evidence from geochemical and iron isotopic data

Iron isotope compositions of various Fe pools in aquifer sediments were measured at a known As-contaminated site in the Datong Basin, China. The δ⁵⁶Fe values of HCl-extracted poor-crystalline Fe(III) range widely from ?0.41‰ to 0.36‰. We interpret the low Fe(II)/Fe_Extractable ratios (<50%) and the negative correlation between Fe(II)/Fe_Extractable and δ⁵⁶Fe values in HCl-extracted poor-crystalline Fe to be best explained by redox cycling of Fe induced by microbial Fe(III) reduction. However, the high Fe(II)/Fe_Extractable ratios (?70%) and positive correlation between Fe(II)/Fe_Extractable and δ⁵⁶Fe values for HCl-extracted poor-crystalline Fe indicates production of sulfides (FeSs). The δ⁵⁶Fe values of crystalline Fe(III) extracted by reductant appears to be comparatively small varying from ?0.01‰ to 0.24‰, which is consistent with the δ⁵⁶Fe values for ferric oxides/hydroxides having undergone microbial Fe(III) reduction. The Fe isotope composition of various Fe pools shows the transformation between crystalline Fe(III) and poor-crystalline crystalline Fe(III) and the secondary Fe(II) phases has already occurred or is occurring in aquifer sediments. More importantly, there is a significant difference in the As concentrations in crystalline Fe(III) oxides/hydroxides and HCl-extracted Fe phases. The concentrations of As range from 1.6 to 29.9 mg kg^?1 and from 0.6 to 3.0 mg kg^?1, for crystalline Fe(III) and HCl-extracted Fe phases respectively. Accordingly, the transformation of Fe minerals induced by microbial Fe(III) reduction can contribute to the mobilization of As. This study is the first to examine the Fe isotope compositions in high As aquifer sediments; the results show that the Fe isotope would be an important tool in demonstrating the enrichment of As in groundwater.     

Arsenic strongly associates with ferrihydrite colloids formed in a soil effluent

Arsenic mobility may increase in liquid phase due to association with colloidal Fe oxides. We studied the association of As with Fe oxide colloids in the effluent from water-saturated soil columns run under anoxic conditions. Upon exfiltration, the solutions, which contained Fe²⁺, were re-aerated and ferrihydrite colloids precipitated. The entire amount of effluent As was associated with the ferrihydrite colloids, although PO₄³⁻, SiO₄⁴⁻, CO₃²⁻ and dissolved organic matter were present in the effluent during ferrihydrite colloid formation. Furthermore, no subsequent release of As from the ferrihydrite colloids was observed despite the presence of these (in)organic species known to compete with As for adsorption on Fe oxides. Arsenic was bound via inner-sphere complexation on the ferrihydrite surface. FTIR spectroscopy also revealed adsorption of PO₄³⁻ and polymerized silica. However, these species could not impede the quantitative association of As with colloidal ferrihydrite in the soil effluents.     

Mobility of heavy metals from polluted sediments of a semi-enclosed basin: in situ benthic chamber experiments in Taranto’s Mar Piccolo (Ionian Sea,Southern Italy)

In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment–water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 μg m^?2 day^?1) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.     

Geochemistry of high arsenic groundwater in Chia-Nan plain, Southwestern Taiwan: possible sources and reactive transport of arsenic

Major ion, trace element, and stable isotope analyses were performed on groundwater samples collected during November 2005 and 2006 in Chia-Nan plain of southwestern Taiwan to examine As mobilization in aquifers. The high concentrations of As, Fe and Mn in the groundwater is consistent with low Eh values (under moderately reduced state). Moreover, the observed Na/Cl and SO(4)/Cl molar ratios in groundwater demonstrate the influence of seawater intrusion. Seawater intrusion could provide required electron acceptors (i.e., SO(4)) for bacterial sulfate reduction and promote reducing conditions that are favorable for As mobilization. The concurrent increases in the concentrations of Fe and Mn from 2005 to 2006 may be caused by bacterial Fe(III) and Mn(IV) reduction. Geochemical modeling demonstrate that As(III) is the dominant As species and the presence of Fe-bearing carbonates, sulfides, and oxide phases may locally act as potential sinks for As. Mud volcano fluids were also collected and analyzed to assess the possible source of As in the Chia-Nan plain groundwater. The oxygen and hydrogen isotopic signatures indicate that the As-rich mud volcano fluids may have been modified by chemical exchange with (18)O-rich crustal rocks and possibly originated from mixing of deep brines with circulating meteoric water. Thus As in the Chia-Nan plain groundwater may have been evolved from deep crustal fluids or rock sources. The hydrogeochemistry and widespread As enrichment in groundwater of Chia-Nan plain result from multiple processes, e.g., de-watering of deep crustal fluids, seawater intrusion, and biogeochemical cycling of Fe, As, and S in alluvial sediments.     

Characterization of shallow groundwater quality in the Lower St. Johns River Basin: a case study

Characterization of groundwater quality allows the evaluation of groundwater pollution and provides information for better management of groundwater resources. This study characterized the shallow groundwater quality and its spatial and seasonal variations in the Lower St. Johns River Basin, Florida, USA, under agricultural, forest, wastewater, and residential land uses using field measurements and two-dimensional kriging analysis. Comparison of the concentrations of groundwater quality constituents against the US EPA’s water quality criteria showed that the maximum nitrate/nitrite (NO _x ) and arsenic (As) concentrations exceeded the EPA’s drinking water standard limits, while the maximum Cl, SO ₄ ^2?? , and Mn concentrations exceeded the EPA’s national secondary drinking water regulations. In general, high kriging estimated groundwater NH ₄ ⁺ concentrations were found around the agricultural areas, while high kriging estimated groundwater NO _x concentrations were observed in the residential areas with a high density of septic tank distribution. Our study further revealed that more areas were found with high estimated NO _x concentrations in summer than in spring. This occurred partially because of more NO _x leaching into the shallow groundwater due to the wetter summer and partially because of faster nitrification rate due to the higher temperature in summer. Large extent and high kriging estimated total phosphorus concentrations were found in the residential areas. Overall, the groundwater Na and Mg concentration distributions were relatively more even in summer than in spring. Higher kriging estimated groundwater As concentrations were found around the agricultural areas, which exceeded the EPA’s drinking water standard limit. Very small variations in groundwater dissolved organic carbon concentrations were observed between spring and summer. This study demonstrated that the concentrations of groundwater quality constituents varied from location to location, and impacts of land uses on groundwater quality variation were profound.     

Engineered in situ bioremediation of a petroleum hydrocarbon-contaminated aquifer: assessment of mineralization based on alkalinity, inorganic carbon and stable carbon isotope balances

A concept is proposed to assess in situ petroleum hydrocarbon mineralization by combining data on oxidant consumption, production of reduced species, CH₄, alkalinity and dissolved inorganic carbon (DIC) with measurements of stable isotope ratios. The concept was applied to a diesel fuel contaminated aquifer in Menziken, Switzerland, which was treated by engineered in situ bioremediation. In the contaminated aquifer, added oxidants (O₂ and NO₃⁻) were consumed, elevated concentrations of Fe(II), Mn(II), CH₄, alkalinity and DIC were detected and the DIC was generally depleted in ¹³C compared to the background. The DIC production was larger than expected based on the consumption of dissolved oxidants and the production of reduced species. Stable carbon isotope balances revealed that the DIC production in the aquifer originated mainly from microbial petroleum hydrocarbon mineralization, and that geochemical reactions such as carbonate dissolution produced little DIC. This suggests that petroleum hydrocarbon mineralization can be underestimated if it is determined based on concentrations of dissolved oxidants and reduced species.     

A laboratory-incubated redox oscillation experiment to investigate Hg fluxes from highly contaminated coastal marine sediments (Gulf of Trieste,Northern Adriatic Sea)

Mercury (Hg) mobility at the sediment–water interface was investigated during a laboratory incubation experiment conducted with highly contaminated sediments (13 μg g^-1) of the Gulf of Trieste. Undisturbed sediment was collected in front of the Isonzo River mouth, which inflows Hg-rich suspended material originating from the Idrija (NW Slovenia) mining district. Since hypoxic and anoxic conditions at the bottom are frequently observed and can influence the Hg biogeochemical behavior, a redox oscillation was simulated in the laboratory, at in situ temperature, using a dark flux chamber. Temporal variations of several parameters were monitored simultaneously: dissolved Hg (DHg) and methylmercury (MeHg), O₂, NH₄ ⁺, NO₃ ^- + NO₂ ^-, PO₄ ^3-, H₂S, dissolved Mn²⁺, dissolved inorganic and organic carbon (DIC and DOC). Under anoxic conditions, both Hg (665 ng m² day^-1) and MeHg (550 ng m² day^-1) fluxed from sediments into the water column, whereas re-oxygenation caused concentrations of MeHg and Hg to rapidly drop, probably due to re-adsorption onto Fe/Mn-oxyhydroxides and enhanced demethylation processes. Hence, during anoxic events, sediments of the Gulf of Trieste may be considered as an important source of DHg species for the water column. On the contrary, re-oxygenation of the bottom compartment mitigates Hg and MeHg release from the sediment, thus acting as a natural “defence” from possible interaction between the metal and the aquatic organisms.     

X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by Fe-bearing minerals

The long-lived radionuclide ⁷⁹Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (Se^VIO₄²⁻) and selenite (Se^IVO₃²⁻). Previous investigations have demonstrated, however, that Se^IV and Se^VI are reduced by surface-associated Fe^II, thereby forming insoluble Se⁰ and Fe selenides. Here we show that the mixed Fe^II/^III (hydr)oxides green rust and magnetite, and the Fe^II sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the Fe^II carbonate siderite produces elemental Se. In the case of mackinawite, both S^−II and Fe^II surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these Fe^II systems is controlled by the concentration of HSe⁻; Se⁰ forms only at lower HSe⁻ concentrations related to slower HSeO₃⁻ reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe²⁺-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 × 10^− 8 M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since Fe^II phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product ⁷⁹Se may be much lower than previously assumed.     

Quaternary stratigraphy, sediment characteristics and geochemistry of arsenic-contaminated alluvial aquifers in the Ganges–Brahmaputra floodplain in central Bangladesh

This study focuses on the Quaternary stratigraphy, sediment composition, mineralogy, and geochemistry of arsenic (As)-contaminated alluvial aquifers in the Ganges–Brahmaputra floodplain in the central Bangladesh. Arsenic concentrations in 85 tubewells in Manikganj area, 70 km northwest of Dhaka City, range from 0.25 µg/L to 191 µg/L with a mean concentration of 33 µg/L. Groundwater is mainly Ca–HCO₃ type with high concentrations of dissolved As, Fe, and Mn, but low level of SO₄. The uppermost aquifer occurs between 10 m and 80 m below the surface that has a mean arsenic concentration of 35 µg/L. Deeper aquifer (> 100 m depth) has a mean arsenic concentration of 18 µg/L. Sediments in the upper aquifer are mostly gray to dark-gray, whereas sediments in the deep aquifer are mostly yellowing-gray to brown. Quartz, feldspar, mica, hornblende, garnet, kyanite, tourmaline, magnetite, ilmenite are the major minerals in sediments from both aquifers. Biotite and potassium feldspar are dominant in shallow aquifer, although plagioclase feldspar and garnet are abundant in deep aquifer sediments. Sediment composition suggests a mixed provenance with sediment supplies from both orogenic belts and cratons. High arsenic concentrations in sediments are found within the upper 50 m in drilled core samples. Statistical analysis shows that As, Fe, Mn, Ca, and P are strongly correlated in sediments. Concentrations of Cd, Cu, Ni, Zn, and Bi also show strong correlations with arsenic in the Manikganj sediment cores. Authigenic goethite concretions, possibly formed by bacteria, are found in the shallow sediments, which contain arsenic of a concentration as high as 8.8 mg/kg. High arsenic concentrations in aquifers are associated with fine-grained sediments that were derived mostly from the recycled orogens and relatively rapidly deposited mainly by meandering channels during the Early to Middle Holocene rising sea-level conditions.     

Comparative effects on arsenic uptake between iron (hydro)oxides on root surface and rhizosphere of rice in an alkaline paddy soil

The iron (Fe) (hydro)oxides deposited around rice roots play an important role in arsenic (As) sequestration in paddy soils, but there is no systematic study on the relative importance of Fe (hydro)oxides on root surface and in rhizosphere soil in limiting As bioavailability. Twenty-seven rice genotypes were selected to investigate effects of Fe (hydro)oxides on As uptake by rice in an alkaline paddy soil. Results indicated that the As content was positively correlated with the Fe content on root surface, and most of As (88–97%) was sequestered by poorly crystalline and crystalline Fe (hydro)oxides in the alkaline paddy soil. The As sequestration by Fe (hydro)oxides on root surface (IAS_root 16.8–25.0 mg As/(g Fe)) was much higher than that in rhizosphere (IAS_rhizo 1.4–2.0 mg As/(g Fe)); therefore, in terms of As immobilization, the Fe (hydro)oxides on root surface were more important than that in rhizosphere. However, the As content in brown rice did not have significant correlation with the As content on root surface but was significantly correlated (R²?=?0.43, P?<?0.05) with the partition ratio (PR_As?=?IAS_root/IAS_rhizo) of As sequestration on root surface and in rhizosphere, which suggested that Fe (hydro)oxides on root surface did not play the controlling role in lowering As uptake, and the partition ratio PR_As would be a better indicator to evaluate effects of Fe (hydro)oxides around roots on As uptake by rice.

     

Redundancy analysis for characterizing the groundwater quality in coastal industrial areas

Groundwater quality in coastal area has been an issue of interest because of excessive groundwater extraction for human use, for example, industrialization, irrigation, which can lead to saltwater intrusion. The study develops an integrated data analysis procedure based on multivariate statistics principal component analysis (PCA), hierarchical cluster analysis (HCA) and redundancy analysis (RDA), to determine the effects of key environmental conditions on the formulation of groundwater pollutants. This proposed method was demonstrated by analyzing groundwater quality monitoring data collected between 2011 and 2014 from four coastal industrial areas in Changhua county of Taiwan, namely Chuansing, Xianxi, Lukang and Fangyuan industrial parks. First, different environmental conditions in each industrial region were explored by PCA. The spatial hierarchy and spatial distribution of pollutant categories were then identified using HCA with the kriging method. Finally, the effect of environmental conditions on constitutive pollutants were identified with RDA. The three environmental patterns identified from the analytical results in Chuansing, Lukang and Xianxi were the salination factor (including conductivity and general hardness (GH)), water level and redox condition (including dissolved oxygen and oxidation–reduction potential). Fangyuan industrial park had only two patterns, namely salination (including conductivity and GH) and oxygen content (including DO and depth). The pollutant category indicated high concentrations of all pollutants in Chuansing and Fangyuan, and higher concentration of SO₄^2?, TDS, Cl^? in Xianxi, and of NH₃-N, Mn, Fe and TOC in Lukang. According to RDA results, salination caused the high concentrations of NH₃N, Cl^?, TDS in Chuansing, and of Cl^?, TDS and SO₄^2? in Xianxi and Lukang. Additionally, salination caused high concentrations of Fe in both Lukang and Fangyuan industrial parks in combination with those three pollutants. The redox condition was linked to high content of NO₃^? in Chuansing and Lukang, and of TOC in Xianxi. In Fangyuan industrial park, NO₃^? was also linked to high oxygen concentration. In summary, the combination of PCA, HCA and RDA enables the analysis of monitoring data to support policy decision-making.     

Natural and anthropogenic factors affecting the groundwater quality in the Nandong karst underground river system in Yunan, China

The Nandong Underground River System (NURS) is located in a typical karst agriculture dominated area in the southeast Yunnan Province, China. Groundwater plays an important role for social and economical development in the area. However, with the rapid increase in population and expansion of farm land, groundwater quality has degraded. 42 groundwater samples collected from springs in the NURS showed great variation of chemical compositions across the study basin. With increased anthropogenic contamination in the area, the groundwater chemistry has changed from the typical Ca–HCO₃ or Ca (Mg)–HCO₃ type in karst groundwater to the Ca–Cl (+ NO₃) or Ca (Mg)–Cl (+ NO₃), and Ca–Cl (+ NO₃ + SO₄) or Ca (Mg)–Cl (+ NO₃ + SO₄) type, indicating increases in NO₃⁻, Cl⁻ and SO₄²⁻ concentrations that were caused most likely by human activities in the region. This study implemented the R-mode factor analysis to investigate the chemical characteristics of groundwater and to distinguish the natural and anthropogenic processes affecting groundwater quality in the system. The R-mode factor analysis together with geology and land uses revealed that: (a) contamination from human activities such as sewage effluents and agricultural fertilizers; (b) water–rock interaction in the limestone-dominated system; and (c) water–rock interaction in the dolomite-dominated system were the three major factors contributing to groundwater quality. Natural dissolution of carbonate rock (water–rock interaction) was the primary source of Ca²⁺ and HCO₃⁻ in groundwater, water–rock interaction in dolomite-dominated system resulted in higher Mg²⁺ in the groundwater, and human activities were likely others sources. Sewage effluents and fertilizers could be the main contributor of Cl⁻, NO₃⁻, SO₄²⁻, Na⁺ and K⁺ to the groundwater system in the area. This study suggested that both natural and anthropogenic processes contributed to chemical composition of groundwater in the NURS, human activities played the most important role, however.