Rare-earth elements in iron-manganese concretions from some New Zealand soils

Iron-manganese concretions and their surrounding soil materials from six sites in New Zealand have been analysed for rare-earth elements (REE). The samples studied fall into two groups: (1) those in which Ce is the only REE enriched in the concretions relative to the surrounding soil materials; and (2) those in which all REE are enriched in the concretions relative to the surrounding soil materials and in which Ce and Tb show consistently higher degrees of enrichment than do other REE. Comparison of enrichment factors (i.e., concentration in concretions/concentration in surrounding soil materials) indicates that Ce and total REE enrichment is related to Mn rather than Fe enrichment in concretions. Other trace element results show that As is enriched in all the concretion samples.     

新疆塔城盆地地下水中铁锰分布特征及人类活动的影响

以新疆塔城盆地80组地下水样品水化学组分测试结果为依据,结合区域地质、水文地质调查资料,研究塔城盆地地下水中铁、锰分布特征及其成因。结果表明,研究区浅层地下水中铁、锰浓度总体较低,局部超标,其空间分布特征基本一致。对比2017年发布的地下水质量标准,地下水中铁、锰超标率依次为25%和5%,深层承压水铁、锰含量均未超标。地下水中铁锰离子浓度受原生地质环境所控,同时叠加人类活动影响,城镇周边人口密集区尤其是排污沟渠附近地下水中耗氧量、溶解性总固体、铁、锰含量明显升高。地下水中铁锰超标连片区域呈条带状或斑块状分布于塔城盆地北部山区、中部冲积平原区以及南部低山丘陵区的铜钼成矿带,受人类活动影响,在塔城市、额敏县及其周边的地表水和地下水重污染区分布有地下水铁、锰重污染点,污染物特别是有机污染物排放所引起的还原环境促使地层中难溶的铁锰矿物的溶解释放。地层中,尤其是矿床及周边地层中高含量的铁锰是地下水中铁锰的重要来源,沉积层中富含丰富的有机质同时叠加人类活动输入所形成的还原条件是研究区地下水中铁、锰迁移和富集的主控因素。     

Metal contamination of soils at Scott Base,Antarctica

Soil samples taken from excavated pits on traverses across New Zealand’s Scott Base, Antarctica, were leached with water and 0.01 M HNO₃ and the leachates analysed for Ag, Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn. The soils had high conductivity and pH values generally increasing with depth and in the range 8.3–10.1. The water leachate generally contained most of the extractable metals except Mn and Cd, and As. Linear relationships were observed between some metals leached into alkaline solution and the Fe in those solutions. The ratios to Fe were comparable to those of the host basanite, and this observation is interpreted as showing that these metals are incorporated in fine mineral particulates derived directly from the rock mass. Outliers in leachable metal concentrations in the soils indicated appreciable contamination of the soil from anthropogenic sources with Ag, Cd, Cu, Pb and Zn as well as As. In some locations high concentrations of Ag and Cd correspond to specific sources and drainage channels. High concentrations of Pb were widely spread and in the top soil layers whereas the elevated concentrations of Zn were distributed throughout the soil profiles indicating atmospheric sources and different mobilities within the soils. Transport within the soils is evident for some metals, as is lateral movement over and through the soils.     

Geochemical processes controlling arsenic mobility in groundwater: A case study of arsenic mobilization and natural attenuation

The behavior of As in the subsurface environment was examined along a transect of groundwater monitoring wells at a Superfund site, where enhanced reductive dechlorination (ERD) is being used for the remediation of groundwater contaminated with chlorinated solvents. The transect was installed parallel to the groundwater flow direction through the treatment area. The ERD technology involves the injection of organic C (OC) to stimulate in situ microbial dechlorination processes. A secondary effect of the ERD treatment at this site, however, is the mobilization of As, as well as Fe and Mn. The concentrations of these elements are low in groundwater collected upgradient of the ERD treatment area, indicating that, in the absence of the injected OC, the As that occurs naturally in the sediment is relatively immobile. Batch experiments conducted using sediments from the site inoculated with an Fe(III)- and As(V)-reducing bacterium and amended with lactate resulted in mobilization of As, Fe and Mn, suggesting that As mobilization in the field is due to microbial processes.     

Characterization of accumulated precipitates during subsurface iron removal

The principle of subsurface iron removal for drinking water supply is that aerated water is periodically injected into the aquifer through a tube well. On its way into the aquifer, the injected O₂-rich water oxidizes adsorbed Fe²⁺, creating a subsurface oxidation zone. When groundwater abstraction is resumed, the soluble Fe²⁺ is adsorbed and water with reduced Fe concentrations is abstracted for multiple volumes of the injection water. In this article, Fe accumulation deposits in the aquifer near subsurface treatment wells were identified and characterized to assess the sustainability of subsurface iron removal regarding clogging of the aquifer and the potential co-accumulation of other groundwater constituents, such as As. Chemical extraction of soil samples, with Acid-Oxalate and HNO₃, showed that Fe had accumulated at specific depths near subsurface iron removal wells after 12 years of operation. Whether it was due to preferred flow paths or geochemical mineralogy conditions; subsurface iron removal clearly favoured certain soil layers. The total Fe content increased between 11.5 and 390.8 mmol/kg ds in the affected soil layers, and the accumulated Fe was found to be 56-100% crystalline. These results suggest that precipitated amorphous Fe hydroxides have transformed to Fe hydroxides of higher crystallinity. These crystalline, compact Fe hydroxides have not noticeably clogged the investigated well and/or aquifer between 1996 and 2008. The subsurface iron removal wells even need less frequent rehabilitation, as drawdown increases more slowly than in normal production wells. Other groundwater constituents, such as Mn, As and Sr were found to co-accumulate with Fe. Acid extraction and ESEM-EDX showed that Ca occurred together with Fe and by X-ray Powder Diffraction it was identified as calcite.     

Distribution of iron in the surface and groundwaters of East Godavari district,Andhra Pradesh,India

With the progradation of Godavari delta in the east coast of India, increase in iron (Fe) concentrations in the groundwater was observed. High concentrations of Fe (>10 mg/l) were observed in khondalite and charnockite formations. A lower portion of the Godavari river basin, viz. East Godavari district was chosen for the study of the distribution of iron with special reference to the existing geological formations and the geomorphology of the area. The concentration of iron was observed to vary from below detection limit to 69 mg/l in the groundwater while it was less than 1 mg Fe/l in river and spring waters. The Fe of river water was reduced due to seawater mixing and the electrical conductivity (EC) was increased approximately to half of the seawater conductivity. Unlike the mixing of seawater at the surface, the same seawater mixing with groundwater yielded a water having similar order of EC with relatively high Fe. Fe was inversely related with nitrate in the groundwater. Fe was found to correlate considerably better with manganese in fluvial and coastal alluvium zones. The locations having higher Fe in delta are suspected to be related to palaeo channels. The association between Fe and Mn and their negative association with NO₃ may be due to the possible autotrophic denitrification that might have taken place in the subsurface.     

The chemistry of suspended matter in Esthwaite Water,a biologically productive lake with seasonally anoxic hypolimnion

Ten detailed vertical water column profiles were taken between April and November, 1979, in Esthwaite Water (English Lake district), a lake with high biological productivity and a seasonally anoxic hypolimnion. Measurements of the major-element particle composition (organic C, P, S, Si, Al, Ti, K, Mg, Ca, Fe, Mn, and Ba) and hydrochemical constituents (temperature, pH, dissolved oxygen, total suspended load, dissolved Fe, Mn, P, and Ba) were carried out. These have revealed new information about the mechanisms and kinetics of biogeochemical cycles in a lake.Pronounced seasonal cycles exist in which large excess concentrations (those unsupported by detrital components) of particulate organic C, Fe, Mn, P, S, Mg, K, Ba, and Ca are being generated and lost in situ in the water column (15m deep). In the epilimnion these elements (excepting Fe and Mn) are incorporated into the organic components of growing phytoplankton during the spring and summer. Simultaneously, in the hypolimnion there is a build-up and then a decrease in the excess concentrations of particulate C, P, S, Mg, K, Ba and Ca; this cycle is due to the indirect involvement of these elements with the iron redox cycle. As the hypolimnion becomes anoxic, dissolved ferrous Fe is released from the sediments and large concentrations of excess particulate iron (III) oxides accumulate; these oxides act as adsorbing substrates for the above mentioned elements. As conditions become more reducing, these same elements are solubilized as the iron (III) oxide particles are reduced to dissolved ferrous iron.Adsorption equations are derived from the field data which relate the concentration of excess particulate Fe to those of POC, P, S, Ca, Mg, Ba, and K. At the last stages of anoxia (before the lake overturns) large populations of bacteria and the formation of iron sulfide particles control the concentrations of excess particulate C, S, P, Mg, K, and Ca.     

Biogeochemistry of iron oxidation in a circumneutral freshwater habitat

Iron(II) oxidation in natural waters at circumneutral pH, often regarded as an abiotic process, is frequently biologically mediated at iron-rich redox gradients. West Berry Creek, a small circumneutral tributary that flows through a mixed coniferous forest in Big Basin State Park, California, contains localized iron (hydr)oxide precipitates at points along its course where anoxic groundwater meets oxygenated creek water. These mixing zones establish redox gradients that may be exploited by microbes forming microbial mats that are intimately associated with iron (hydr)oxide precipitates. Water sampling revealed strong correlations between the concentrations of aqueous inorganic species, suggesting a rock-weathering source for most of these solutes. Liquid chromatography–electrospray ionization–mass spectrometry techniques detected significant concentrations of organic exudates, including low molecular mass organic acids and siderophores, indicating that active biogeochemical cycling of iron is occurring in the creek. X-ray diffraction and elemental analysis showed the precipitates to be amorphous, or possibly poorly crystalline, iron-rich minerals. Clone libraries developed from 16S rDNA sequences extracted from microbial mat communities associated with the precipitates revealed the presence of microorganisms related to the neutrophilic iron oxidizing bacteria Gallionella and Sideroxydans. Sequences from these libraries also indicated the presence of significant populations of organisms related to bacteria in the genera Aquaspirillum, Pseudomonas, Sphingomonas, and Nitrospira. These geosymbiotic systems appear to be significant not only for the biogeochemical cycling of iron in the creek, but also for the cycling of organic species, inorganic nutrients, and trace metals.     

Increased concentrations of potassium in heartwood of trees in response to groundwater contamination

The wood of tuliptrees (Liriodendron tulipifera L.) growing above groundwater contamination from a hazardous-waste landfill in Maryland contained elevated concentrations of potassium (K). The groundwater contamination also contained elevated concentrations of dissolved K, as well as arsenic (As), cadmium (Cd), chloride (Cl), iron (Fe), manganese (Mn), zinc (Zn), and organic solvents. The dissolved K is derived from disposed smoke munitions. The excess K in the tuliptrees is concentrated in the heartwood, the part of the xylem most depleted in K in trees growing outside of the contamination. These data show that the uptake and translocation of K by tuliptrees can be strongly influenced by the availability of K in groundwater contamination and suggest the utility of this species as an areal indicator of groundwater contamination.     

Composition of manganese nodules and manganese carbonates from Loch Fyne,Scotland

Manganese nodules and manganese carbonate concretions occur in the upper 10–15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180–200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5–8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments.The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn.The manganese carbonate has the composition (Mn_47.7 Ca_45.1 Mg_7.2) CO₃. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice.Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations.     

Structural constraints of ferric (hydr)oxides on dissimilatory iron reduction and the fate of Fe(II)

Due to the strong reducing capacity of ferrous Fe, the fate of Fe(II) following dissimilatory iron reduction will have a profound bearing on biogeochemical cycles. We have previously observed the rapid and near complete conversion of 2-line ferrihydrite to goethite (minor phase) and magnetite (major phase) under advective flow in an organic carbon-rich artificial groundwater medium. Yet, in many mineralogically mature environments, well-ordered iron (hydr)oxide phases dominate and may therefore control the extent and rate of Fe(III) reduction. Accordingly, here we compare the reducing capacity and Fe(II) sequestration mechanisms of goethite and hematite to 2-line ferrihydrite under advective flow within a medium mimicking that of natural groundwater supplemented with organic carbon. Introduction of dissolved organic carbon upon flow initiation results in the onset of dissimilatory iron reduction of all three Fe phases (2-line ferrihydrite, goethite, and hematite). While the initial surface area normalized rates are similar (∼10⁻¹¹ mol Fe(II) m⁻² g⁻¹), the total amount of Fe(III) reduced over time along with the mechanisms and extent of Fe(II) sequestration differ among the three iron (hydr)oxide substrates. Following 16 d of reaction, the amount of Fe(III) reduced within the ferrihydrite, goethite, and hematite columns is 25, 5, and 1%, respectively. While 83% of the Fe(II) produced in the ferrihydrite system is retained within the solid-phase, merely 17% is retained within both the goethite and hematite columns. Magnetite precipitation is responsible for the majority of Fe(II) sequestration within ferrihydrite, yet magnetite was not detected in either the goethite or hematite systems. Instead, Fe(II) may be sequestered as localized spinel-like (magnetite) domains within surface hydrated layers (ca. 1 nm thick) on goethite and hematite or by electron delocalization within the bulk phase. The decreased solubility of goethite and hematite relative to ferrihydrite, resulting in lower Fe(III)_aq and bacterially-generated Fe(II)_aq concentrations, may hinder magnetite precipitation beyond mere surface reorganization into nanometer-sized, spinel-like domains. Nevertheless, following an initial, more rapid reduction period, the three Fe (hydr)oxides support similar aqueous ferrous iron concentrations, bacterial populations, and microbial Fe(III) reduction rates. A decline in microbial reduction rates and further Fe(II) retention in the solid-phase correlates with the initial degree of phase disorder (high energy sites). As such, sustained microbial reduction of 2-line ferrihydrite, goethite, and hematite appears to be controlled, in large part, by changes in surface reactivity (energy), which is influenced by microbial reduction and secondary Fe(II) sequestration processes regardless of structural order (crystallinity) and surface area.     

长江口氧化还原敏感元素的早期成岩过程

通过测试长江口沉积物及间隙水中Fe、Mn、U及Mo的含量,结合早期成岩模型及地球化学热力学分析,探讨了在河口环境中影响间隙水氧化还原敏感元素(Fe、Mn、U及Mo)分布的主要因素.根据Fick第一定律,估算了Fe、Mn、U及Mo在沉积物-水界面的扩散通量.结果表明,间隙水Fe、Mn、U及Mo的含量分别介于0.8~106μmol/L、14.8~258μmol/L、1.9~14.4nmol/L及60~546nmol/L之间.在垂直剖面上,间隙水Fe、Mn峰值分别出现在约5cm或10cm的深度.早期成岩过程是影响长江口沉积物间隙水Fe、Mn分布的主要因素.吸附系数对间隙水Fe、Mn的分布也有重要的影响.吸附系数越高,间隙水Fe、Mn浓度越低.影响间隙水U分布的主要因素为Fe,而Mo与Fe、Mn之间不存在相关性.通量计算结果显示Fe、Mn、U及Mo的扩散通量分别介于3.0~10.5μmol·(m2·d)-1、35.7~439.5μmol·(m2·d)-1、-2.3~0.2nmol·(m2·d)-1及-36.0~94.6nmol·(m2·d)-1之间.沉积物中自生铀组分约占总铀的6%~67%.      

Iron concretions within a highly altered unit of the Berlins Porphyry,New Zealand: an abiotic or biotic story?

Mineralogy and Petrology - The Berlins Porphyry located on the South Island of New Zealand provides an opportunity to examine iron concretions formed in a subterranean system. Specifically, an...     

A comparison of the early diagenetic environment in intertidal sands and muds of the Manukau Harbour,New Zealand

The early diagenetic environment of intertidal sandy sediments (sands) and muddy sediments (muds) is described and compared from two cores taken from an unpolluted part of the Manukau Harbour, New Zealand. Extraction techniques characterized the form of the trace elements (Fe, Mn, S, C, Pb, Zn, Cu) at different depths in the sediment. Dissolved forms of Fe, Mn, and S were measured in interstitial water. Nonresidual metal concentrations, humic acid, FeS, and FeS₂ are an order of magnitude higher in the muds than in the sands because of dilution by unreactive sand particles. Muds contain a larger proportion of metals in the mobile fractions; exchangeable (Mn), carbonate (Mn, Fe, Zn), and easily-reducible oxide (Fe, Mn, Zn, Pb). This is due to greater surface area (for Mn adsorption); the favorable conditions for MnCO₃, FeCO₃, and FeS precipitation; and higher concentrations of easily reducible iron oxide and humic acid. Therefore, compared to the sands, muds are more important as reservoirs for toxic metals, both in terms of quantity and availability. At either site there was very little difference between the forms of Zn, Pb or Cu identified by sequential extraction as sediments changed from oxic to anoxic conditions. One reason for this is that the amounts and proportions of some of the important components that bind metals, viz., amorphous iron hydrous oxides, humic acids, and FeS₂, do not change much. Other components that do change with redox conditions, for example, manganese phases and FeS, are only minor components of the sediment. Redox conditions, then, have relatively little effect on trace-metal partitioning in the sediment matrix of these unpolluted sediments.     

江汉平原东北部地区高铁锰地下水成因与分布规律

肖港地区位于江汉平原东北部,属于大别山连片贫困区和贫水区,地下水资源较贫乏,且地下水水质不佳,水中铁锰离子含量普遍超过了国家饮用水标准。为查明高铁锰地下水成因及空间分布规律,服务区内地下水开发利用及安全供水问题,系统采集区内岩石、土壤和地下水样品,测试岩土与地下水中铁锰的含量,分析地下水中铁锰含量与含水层沉积物的铁锰含量、地下水的氧化还原条件和酸碱度之间的关系。结果表明:江汉平原东北部地区地下水中铁锰超标现象普遍存在,其中锰的超标率大于铁,第四系孔隙潜水超标最严重,铁锰最大浓度分别达到44.88 mg/L和19.21 mg/L。研究区岩土中铁锰氧化物为地下水中铁锰提供了物质来源,弱酸性、强还原环境为沉积物中铁锰的溶解释放提供了有利条件,总体上从研究区东西两侧（补给、径流区）向中部第四系孔隙潜水含水层（排泄区）,沿地下水流向Eh值、pH值逐渐减小,铁锰含量逐渐增大,形成北北东向带状分布的高铁锰地下水区。     

Delineation of potentially auriferous quartz reefs by analysis of the bark of Pinus radiata (Monterey pine)

Rocks and bark samples of Pinus radiata from Union Hill, Waihi, New Zealand were analyzed for 19 elements to establish whether the elemental content of bark could be used to delineate subterranean auriferous quartz reefs and veins. Three elemental concentrations in bark (chromium, nickel and sodium) show sufficiently great differences (P < 0.05) between populations growing on or off the reefs (i.e. on quartz reefs or on andesites), to be diagnostic of subterranean potentially auriferous quartz. Gold in the bark not diagnostic although it was correlated with arsenic and iron. It is concluded that the technique should be applicable elsewhere in New Zealand or overseas where P. radiata is to be found growing over potentially auriferous ground.     

Hydrogeochemical characteristics of groundwater and pore-water and the paleoenvironmental evolution in the past 3.10 Ma in the Xiong’an New Area,North China

The groundwater level has been continuously decreasing due to climate change and long-time overexploitation in the Xiong’an New Area, North China, which caused the enhanced mixing of groundwater in different aquifers and significant changes in regional groundwater chemistry characteristics. In this study, groundwater and sediment pore-water in drilling cores obtained from a 600 m borehole were investigated to evaluate hydrogeochemical processes in shallow and deep aquifers and paleo-environmental evolution in the past ca. 3.10 Ma. Results showed that there was no obvious change overall in chemical composition along the direction of groundwater runoff, but different hydrochemical processes occurred in shallow and deep groundwater in the vertical direction. Shallow groundwater (< 150 m) in the Xiong’an New Area was characterized by high salinity (TDS > 1000 mg/L) and high concentrations of Mn and Fe, while deep groundwater had better water quality with lower salinity. The high TDS values mostly occurred in aquifers with depth < 70 m and >500 m below land surface. Water isotopes showed that aquifer pore-water mostly originated from meteoric water under the influence of evaporation, and aquitard pore-water belonged to Paleo meteoric water. In addition, the evolution of the paleoclimate since 3.10 Ma BP was reconstructed, and four climate periods were determined by the δ¹⁸O profiles of pore-water and sporopollen records from sediments at different depths. It can be inferred that the Quaternary Pleistocene (0.78–2.58 Ma BP) was dominated by the cold and dry climate of the glacial period, with three interglacial intervals of warm and humid climate. What’s more, this study demonstrates the possibilities of the applications of pore-water on the hydrogeochemical study and further supports the finding that pore-water could retain the feature of paleo-sedimentary water.© 2021 China Geology Editorial Office.     

Secondary mineralization pathways induced by dissimilatory iron reduction of ferrihydrite under advective flow

Iron (hydr)oxides not only serve as potent sorbents and repositories for nutrients and contaminants but also provide a terminal electron acceptor for microbial respiration. The microbial reduction of Fe (hydr)oxides and the subsequent secondary solid-phase transformations will, therefore, have a profound influence on the biogeochemical cycling of Fe as well as associated metals. Here we elucidate the pathways and mechanisms of secondary mineralization during dissimilatory iron reduction by a common iron-reducing bacterium, Shewanella putrefaciens (strain CN32), of 2-line ferrihydrite under advective flow conditions. Secondary mineralization of ferrihydrite occurs via a coupled, biotic-abiotic pathway primarily resulting in the production of magnetite and goethite with minor amounts of green rust. Operating mineralization pathways are driven by competing abiotic reactions of bacterially generated ferrous iron with the ferrihydrite surface. Subsequent to the initial sorption of ferrous iron on ferrihydrite, goethite (via dissolution/reprecipitation) and/or magnetite (via solid-state conversion) precipitation ensues resulting in the spatial coupling of both goethite and magnetite with the ferrihydrite surface. The distribution of goethite and magnetite within the column is dictated, in large part, by flow-induced ferrous Fe profiles. While goethite precipitation occurs over a large Fe(II) concentration range, magnetite accumulation is only observed at concentrations exceeding 0.3 mmol/L (equivalent to 0.5 mmol Fe[II]/g ferrihydrite) following 16 d of reaction. Consequently, transport-regulated ferrous Fe profiles result in a progression of magnetite levels downgradient within the column. Declining microbial reduction over time results in lower Fe(II) concentrations and a subsequent shift in magnetite precipitation mechanisms from nucleation to crystal growth. While the initial precipitation rate of goethite exceeds that of magnetite, continued growth is inhibited by magnetite formation, potentially a result of lower Fe(III) activity. Conversely, the presence of lower initial Fe(II) concentrations followed by higher concentrations promotes goethite accumulation and inhibits magnetite precipitation even when Fe(II) concentrations later increase, thus revealing the importance of both the rate of Fe(II) generation and flow-induced Fe(II) profiles. As such, the operating secondary mineralization pathways following reductive dissolution of ferrihydrite at a given pH are governed principally by flow-regulated Fe(II) concentration, which drives mineral precipitation kinetics and selection of competing mineral pathways.     

Physiochemical conditions of Folsomia candida occurrence in a shallow coastal Lake Michigan aquifer

An insect, Folsomia candida, was found in a shallow aquifer along the southwestern coast of Michigan. F. candida is a standard organism for soil toxicity testing but its occurrence in groundwater is uncommon to rare, or has been under-reported in the literature. Attempts to correlate the presence of F. candida to water and soil parameters yielded: (1) F. candida is present in the upper 15–25 cm of topsoil, but absent in the underlying vadose zone except directly above the water table, regardless of the presence in groundwater; (2) F. candida is most abundant in groundwater 4.3–5.0 m below land surface; (3) Most F. candida occur in wells with dissolved oxygen ranging from 4 to 5 ppm; (4) F. candida is most abundant in water between about 14 and 18°C; (5) F. candida is abundant in groundwater with high concentrations of Cl⁻, Na⁺, and K⁺; and, (6) Small differences in pore space volume determine the feasibility of F. candida occupancy, but not the presence of F. candida in the study area.     

Trace element cycling in a subterranean estuary: Part 1. Geochemistry of the permeable sediments

Subterranean estuaries are characterized by the mixing of terrestrially derived groundwater and seawater in a coastal aquifer. Subterranean estuaries, like their river water-seawater counterparts on the surface of the earth, represent a major, but less visible, hydrological and geochemical interface between the continents and the ocean. This article is the first in a two-part series on the biogeochemistry of the subterranean estuary at the head of Waquoit Bay (Cape Cod, MA, USA). The pore-water distributions of salinity, Fe and Mn establish the salt and redox framework of this subterranean estuary. The biogeochemistry of Fe, Mn, P, Ba, U and Th will be addressed from the perspective of the sediment composition. A second article will focus on the groundwater and pore-water chemistries of Fe, Mn, U and Ba.Three sediment cores were collected from the head of Waquoit Bay where the coastal aquifer consists of permeable sandy sediment. A selective dissolution method was used to measure the concentrations of P, Ba, U and Th that are associated with “amorphous (hydr)oxides of iron and manganese” and “crystalline Fe and Mn (hydr)oxides.” The deeper sections of the cores are characterized by large amounts of iron (hydr)oxides that are precipitated onto organic C-poor quartz sand from high-salinity pore waters rich in dissolved ferrous iron. Unlike Fe (hydr)oxides, which increase with depth, the Mn (hydr)oxides display midcore maxima. This type of vertical stratification is consistent with redox-controlled diagenesis in which Mn (hydr)oxides are formed at shallower depths than iron (hydr)oxides. P and Th are enriched in the deep sections of the cores, consistent with their well-documented affinity for Fe (hydr)oxides. In contrast, the downcore distribution of Ba, especially in core 3, more closely tracks the concentration of Mn (hydr)oxides. Even though Mn (hydr)oxides are 200-300 times less abundant than Fe (hydr)oxides in the cores, Mn (hydr)oxides are known to have an affinity for Ba which is many orders of magnitude greater than iron (hydr)oxides. Hence, the downcore distribution of Ba in Fe (hydr)oxide rich sediments is most probably controlled by the presence of Mn (hydr)oxides. U is enriched in the upper zones of the cores, consistent with the formation of highly reducing near-surface sediments in the intertidal zone at the head of the Bay. Hence, the recirculation of seawater through this type of subterranean estuary, coupled with the abiotic and/or biotic reduction of soluble U(VI) to insoluble U(IV), leads to the sediments acting as a oceanic net sink of U. These results highlight the importance of permeable sediments as hosts to a wide range of biogeochemical reactions, which may be impacting geochemical budgets on scales ranging from coastal aquifers to the continental shelf.