Assessment of the geochemical reactivity of Fe-DOM complexes in wetland sediment pore waters using a nitroaromatic probe compound

The reductive capacity of Fe(II) present in anoxic sediment pore waters affects biogeochemically significant processes that occur in these environments, such as metal speciation, mineral solubility, nutrient bioavailability, and the transformation of anthropogenic organic compounds. We studied the reduction of pentachloronitrobenzene (PCNB) in natural pore waters to elucidate the reductive capacity of Fe(II) complexes, and monitored the redox-active species responsible for the observed kinetics. Differential pulse polarography (DPP) scans of sediment pore waters from a coastal Lake Erie wetland (Old Woman Creek National Estuarine Research Reserve, Huron, OH) revealed an increase in both Fe(III)-organic and Fe(II) species to a depth of ∼30 cm below the sediment-water interface. Concentrations of dissolved organic matter (DOM) in pore waters increased while pH decreased with depth. We found that Fe(II) was necessary for rapid PCNB reduction (<24 h), and observed faster reduction with increased pH. PCNB reduction in preserved pore waters (acidified to pH 2.5 after pore water extraction and raised to the native pH (6.7-7.6) prior to reaction) was similar to that observed in a model system containing Fe(II) and fulvic acid isolated from this site. Conversely, PCNB reduction in unaltered pore water was significantly slower than that observed in preserved pore water, indicating that the Fe(II) speciation and its reductive capacity differed. DPP scans of pore waters used for kinetic studies confirmed that pH-adjustment affected Fe_T speciation in the pore waters, as the Fe(III)-DOM peak current was lowered or disappeared completely in the preserved pore water samples. These data show that pH-adjustment of pore waters presumably alters both their complexation chemistry and reactivity towards PCNB, and shows how small changes in Fe complexation can potentially affect redox chemistry in anoxic environments. Our results also show that reactive organic Fe(II) complexes are naturally present in wetland sediment pore waters, and that these species are potentially important mediators of Fe(II)/Fe(III) redox biogeochemistry in anoxic sedimentary environments.     

Deciphering As and Cu cycling in sediment pore waters in a large marina (Port Camargue,southern France) using a multi-tracer (Fe,Mn, U,Mo) approach

The sediments of the Port Camargue marina (South of France) are highly polluted by Cu and As (Briant et al., 2013). The dynamics of these pollutants in pore waters was investigated using redox tracers (sulfides, Fe, Mn, U, Mo) to better constrain the redox conditions.In summer, pore water profiles showed a steep redox gradient in the top 24 cm with the reduction of Fe and Mn oxy-hydroxides at the sediment water interface (SWI) and of sulfate immediately below. Below a depth of 24 cm, the Fe, Mn, Mo and U profiles in pore waters reflected Fe and Mn reducing conditions and, unlike in the overlying levels, sulfidic conditions were not observed. This unusual redox zonation was attributed to the occurrence of two distinct sediment layers: an upper layer comprising muddy organic-rich sediments underlain by a layer of relatively sandy and organic-poor sediments. The sandy sediments were in place before the building of the marina, whereas the muddy layer was deposited later. In the muddy layer, large quantities of Fe and Mo were removed in summer linked to the formation of insoluble sulfide phases. Mn, which can adsorb on Fe-sulfides or precipitate with carbonates, was also removed from pore waters. Uranium was removed probably through reduction and adsorption onto particles. In winter, in the absence of detectable pore water sulfides, removal of Mo was moderate compared to summer.Cu was released into solution at the sediment water interface but was efficiently trapped by the muddy layer, probably by precipitation with sulfides. Due to efficient trapping, today the Cu sediment profile reflects the increase in its use as a biocide in antifouling paints over the last 40 years.In the sandy layer, Fe, Mn, Mo and As were released into solution and diffused toward the top of the profile. They precipitated at the boundary between the muddy and sandy layers. This precipitation accounts for the high (75 μg g⁻¹) As concentrations measured in the sediments at a depth of 24 cm.     

Seasonal Influence of the Needle Rush <Emphasis Type="Italic">Juncus roemarianus</Emphasis> on Saltmarsh Pore Water Geochemistry

Previous studies have shown that saltmarsh macrophytes have a significant influence on sediment biogeochemistry, both through radial release of oxygen from roots and also via primary production and release of labile organic exudates from roots. To assess the seasonal influence of the needle rush, Juncus roemarianus, on saltmarsh sediment geochemistry, pore waters and sediments were collected from the upper 50 cm of two adjacent sites, one unvegetated and the other vegetated by Juncus roemarianus, in a Georgia saltmarsh during winter and summer. Pore waters collected at 1- to 2-cm intervals were analyzed for pH, alkalinity, dissolved phosphate, ammonium, Fe(II), Fe(III), Mn(II), sulfide, sulfate, and organic carbon. Sediments were collected at 5-cm intervals and analyzed for iron distribution in the solid phase using a two-step sequential extraction. The upper 50 cm of the sediment pore waters are mostly sulfidic during both winter and summer. The pore water and sediment geochemistry suggest organic matter degradation is coupled mostly to Fe(III) and sulfate reduction. In summer, there is greater accumulation of alkalinity, sulfide, ammonium, and phosphate in the pore waters and lower levels of ascorbate extractable Fe, which is presumed to be comprised primarily of readily reducible Fe(III) oxides, in the sediments, consistent with higher organic matter degradation rates in summer compared to winter. Lower pH, alkalinity, ammonium, and sulfide concentrations in sediments with Juncus, compared to nearby unvegetated sediments, is consistent with release of oxygen into the Juncus rhizosphere, especially during summer.     

Colloidal and truly dissolved metal(oid) fractionation in sediment pore waters using tangential flow filtration

The partitioning of trace metal(oid)s between colloidal and “truly” dissolved fractions in sediment pore waters is often overlooked due to the analytical challenge; indeed, only small volumes are available and filtration membranes are rapidly clogged. Moreover, metal(oid)s are subject to co-precipitate with Fe. In this study, tangential flow filtration (TFF) was assessed for the fractionation of Fe, Mn, Cu, As, Co, Ni, Zn and Cd in sediment pore waters with a 5 kDa cut-off size membrane. Five natural sediments were collected and used for different tests. Results on blank samples showed that this technique was appropriate for Fe, Mn, Co, Zn, As and Cd. Although the applied concentration factors (CF) were low (<7.4) due to the small available volume of pore waters (50 mL), it was shown that colloidal concentrations obtained from the TFF procedure were similar whatever the applied concentration factor. The mass balance approach showed satisfying results (100 ± 25%) for Mn, Co, Zn and As. Mass balances were higher than 130% and highly variable for Cd, Ni and Cu. For Fe, mass balance was reproducible but low (71 ± 10%), probably due to sorption of positively charged Fe oxides on the membrane. Applying this method to five contrasting metal(oid)-contaminated sediments, it was shown that Mn, As, Co and Fe were mainly present in the “truly” dissolved phase (<5 kDa). This technique is a necessary step to assess sediment toxicity and bioavailability of metal(oid)s and could be of great interest for emergent pollutants such as nanometals.     

Element fractionation by sequential extraction in a soil with high carbonate content

The influence of carbonate and other buffering substances in soils on the results of a 3-step sequential extraction procedure (BCR) used for metal fractionation was investigated. Deviating from the original extraction scheme, where the extracts are analysed only for a limited number of metals, almost all elements in the soils were quantified by X-ray fluorescence spectroscopy, in the initial samples as well as in the residues of all extraction steps. Additionally, the mineral contents were determined by X-ray diffractometry. Using this methodology, it was possible to correlate changes in soil composition caused by the extraction procedure with the release of elements. Furthermore, the pH values of all extracts were monitored, and certain extraction steps were repeated until no significant pH-rise occurred. A soil with high dolomite content (27%) and a carbonate free soil were extracted. Applying the original BCR-sequence to the calcareous soil, carbonate was found in the residues of the first two steps and extract pH-values rose by around two units in the first and second step, caused mainly by carbonate dissolution. This led to wrong assignment of the carbonate elements Ca, Mg, Sr, Ba, and also to decreased desorption and increased re-adsorption of ions in those steps. After repetition of the acetic acid step until extract pH remained low, the carbonate was completely destroyed and the distributions of the elements Ca, Mg, Sr, Ba as well as those of Co, Ni, Cu, Zn and Pb were found to be quite different to those determined in the original extraction. Furthermore, it could be shown that the effectiveness of the reduction process in step two was reduced by increasing pH: Fe oxides were not significantly attacked by the repeated acetic acid treatments, but a 10-fold amount of Fe was mobilized by hydroxylamine hydrochloride after complete carbonate destruction. On the other hand, only small amounts of Fe were released anyway. Even repeated reduction steps did not destroy the amorphous Fe oxides completely, showing that 0.1 mol L⁻¹ hydroxylamine hydrochloride was not strong enough to attack these oxides effectively.The extraction sequences were carried out not only on the soil samples, but also on their coarse and fine fractions (> or <2 μm). The fine fraction of the calcareous soil contained only 10% dolomite, but was enriched in organic matter and clay minerals, which also resulted in increased extract pH-values during the sequential extraction. Hence, the effects on ion release in the fine fraction were similar to those of the whole soil. Since the destruction of the organic matter was incomplete after regular oxidation, the H₂O₂-treatment of the fine fraction had to be repeated. The addition of the extractable amounts of the two fractions showed good agreement to the results obtained for extraction of the whole soils. Likewise the pH-values of the carbonate-free soil extracts did not increase significantly, therefore it was concluded that repetitions of extraction steps for this soil were not necessary.Extract-pHs should always be controlled so that extraction conditions are comparable; to be able to use the BCR extraction scheme or similar ones for carbonate- and organic-rich samples this is mandatory. Single extraction steps should be repeated if pH rises too much; additionally the oxidizing step should be performed more than twice for samples rich in organic substances, depending upon the violence of the reaction with H₂O₂. If these precautions are neglected the validity of the extraction data is likely to be questionable.     

Fractionation of heavy metals in bottom sediments using Tessier procedure

The study presents the results of Cu, Pb, Zn, Mn and Fe determination in the samples of bottom sediments collected from the Oder and Warta rivers. The sequential extraction of metals in the samples of bottom sediments was performed after introducing the modification of the extraction scheme suggested by Tessier et al. (Anal Chem 51(7):844–851, 1979). The extraction times of particular stages were optimised. The fifth stage was altered by introducing the new methods of performing extraction. The samples of bottom sediments submitted the following granulometric analyses: dry, wet and wet with (HMP) dispersing reagent. Seven granulometric fractions with the following grain sizes were isolated: >2.0, 2.0–1.0, 1.0–0.5, 0.5–0.25, 0.25–0.1, 0.1–0.063 and <0.063 mm. The sequential extraction of particular granulometric fractions was performed. The concentration of metals variability was analysed depending on the method of sample preparation for the chemical analysis, granulometric fraction of sediments subjected to the analysis, extraction conditions and the site of samples collection. The lack of linearity between the metal concentration and the size of granulometric fraction was observed. The highest concentrations of metals were observed in fractions >2.0, 2.0–1.0 and 0.1–0.063 and <0.063 mm while the lowest concentrations occurred in fractions 1.0–0.5, 0.5–0.25, and 0.25–0.1 mm. The atomic absorption spectrometry with flame atomisation (F-AAS) was used for the determination of the investigated elements.     

Iron isotopes in natural carbonate minerals determined by MC-ICP-MS with a Fe-Fe double spike

We have developed a method for iron isotope analysis by multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) using a ⁵⁸Fe-⁵⁴Fe double spike. A 20 min analysis produces mass-bias-corrected iron isotope data with an external reproducibility of ±0.05 (2 SD) on δ⁵⁶Fe, which represents a decrease in analysis time compared to sample-standard bracketing techniques. The estimation of external reproducibility is based on replicate analysis of the ETH hematite in-house standard. The double spike method has two advantages. First, matrix effects during MC-ICP-MS analysis are decreased with tests showing that accurate iron isotope data can, in some cases, be obtained even when matrix levels exceed iron concentration (Na/Fe, Mg/Fe, and Ca/Fe up to 5, 2, and 0.1, respectively). Because chemical separation reduces matrix/Fe to levels more than three orders of magnitude lower than this, measured Fe isotope compositions are unlikely to be compromised by matrix effects. Second, it is possible to spike samples before chemical purification, which enables any isotopic fractionation effect because of incomplete recovery of iron from a sample to be accounted for. This may be important where obtaining quantitative iron yields from samples is difficult, such as the extraction of dissolved iron from water samples. Fe isotope data on a set of standard reference materials (igneous rocks, ferromanganese nodules, sedimentary rocks, and ores) are presented, which are in agreement with previously published data considering analytical uncertainties. Mantle-derived standard rock samples that are the source of iron for surficial, (bio)geochemical cycling yield a mean δ⁵⁶Fe of 0.041 ± 0.11‰ (n = 8; 2 SD) with reference to IRMM-14. Hydrothermal and metamorphic calcium carbonate rocks with a relatively low iron content (100-4000 ppm) have δ⁵⁶Fe = −1.25 to −0.07‰. Structural Fe(II) in hydrothermal calcites has δ⁵⁶Fe = −1.25 to −0.27‰. The light iron in this range of carbonate minerals may reflect the iron isotope composition of the hydrothermal fluids from which the carbonate precipitated, or the presence of Fe(III) and/or organic material in the hydrothermal fluids during calcite precipitation.     

Pyritization of trace metals in estuarine sediments and the controlling factors: a case in Jiaojiang Estuary of Zhejiang Province,China

Three undisturbed sediment samples were collected from the intertidal zone of the Jiaojiang Estuary of Zhejiang Province, China. The sediments were found to contain remarkably low concentrations of organic carbon (<0.6%) and acid volatile sulfide (AVS) (<30 μmol g⁻¹). The availability of these two substrates likely constrained sulfate reduction and pyritization of several trace metals, respectively. This was especially true at one station where AVS concentrations in the upper 20 cm averaged less than 0.05 μmol g⁻¹. Although the depth dependence of the degree of trace metal pyritization was generally consistent with expectations based on redox conditions, depth profiles of reactive-metal and pyrite-metal concentrations in several cases revealed more complex behavior and a positive correlation between reactive-metal concentrations and pore water metal concentrations.     

A comparative analysis of trace metal pollution parity between sandy and shaly soils: evidence from two mechanic villages in the Imo River basin

Heavy metal enrichment parity in sandy and shaly mechanic village (MV) soils was studied in order to explain the technical and economic imperatives of setting an environmentally friendly MV on either soil. Okigwe (shaly) and Nekede (sandy) mechanic village soils in the Imo River basin Nigeria were tested and compared. Spectroscopic analysis of the soil samples collected from three surface layers (L), where L1: 0–10 cm; L2: 10–20 cm and L3: 90–100 cm shows that Pb > Cu > Mn in the Okigwe MV, and Mn > Pb > Cu in the Nekede MV. Mean concentration of metals (mg kg⁻¹) in Okigwe MV are Fe: 51,291 ± 18,148, Ni: 22 ± 4, Cd: 20 ± 3, Pb: 500 ± 513, Cu: 616 ± 369, Cr: 16 ± 9, and Mn: 378 ± 207. Similarly, Nekede MV has 22,101 ± 7,273 of Fe; 8 ± 0.8 of Ni; 11 ± 4 of Cd; 320 ± 122 of Pb; 265 ± 145 of Cu; 11 ± 2 of Cr; and 350 ± 191 of Mn. Pollution factor (Pf): Okigwe MV has 0.77, and Nekede has 0.68. Pollution degree: Okigwe MV is greater in L1 and L2, while Nekede is greater in L3, with greater potentials for Pb, and Mn mobility than the Okigwe. Both have similar trends of metal distribution, and significant correlation with their background values. Low clay-silt content in Nekede MV soil suggests low sorption capacity, whereas the high clay-silt content (47–64%) of the Okigwe soil suggests lower bioavailability. Infiltration basin is not recommended in a MV on sandy soil if water table is near surface. In such case, the MV must be moved to a location where water table is >37 m, or have clay-shale material transported to the site to form impervious layer base for detention basin. For groundwater safety and sustainability, shaly soils are most recommended for MVs so that detention basin could be economically used for storm water treatment.     

Fractionation of U,Th, Ra and Pb from boreal forest soils by sequential extractions

To determine the mobility of natural radionuclides in boreal forest soil, a five-step sequential extraction procedure was carried out on soil samples taken from various depths down to 3 m on Olkiluoto Island, Finland, where there are plans to construct a spent nuclear fuel disposal repository in the bedrock. The extracted fractions studied were exchangeable, acid-soluble, reducible, oxidizable and tightly bound. It was found that the extractability of most of the radionuclides studied was dependent on the sample grain size and depth. All the elements were concentrated in the smallest grain size samples (<0.063 mm). The extraction behaviour of Th, however, did not vary with sample depth, and only about 10% of the Th was extracted by the time of the final extraction step. Stable Pb and ²¹⁰Pb, as well as Ba and Ra concentrations were strongly correlated in the extractions. Radium and Ba were leached more readily than the other elements; approximately 17% of the total Ra was found in the first fraction extracted, representing exchangeable ions. Uranium was more mobile in the topsoil horizons than in the lower horizons. In the topsoil samples, an average of 51% of the extractable U was leached in the second extraction step, representing the elements soluble in weak acids, whereas only 13% of the U in the subsoil samples was extracted in this step. This is probably due to changes in soil redox conditions lower down the soil profile. The extraction behaviour of Pb and Fe also suggests the presence of more reducing conditions in the deeper soil horizons, because the percentage of extractable Pb and Fe in the oxidizable fraction increased with sample depth.     

The Influence of Extractable Organic Matter on Pore Development in the Late Triassic Chang 7 Lacustrine Shales, Yanchang Formation, Ordos Basin, China

To investigate the influence of extractable organic matter (EOM) on pore evolution of lacustrine shales, Soxhlet extraction, using dichloromethane, was performed on a series of Chang 7 shale samples (Ordos Basin, China) with vitrinite reflectance of 0.64% to 1.34%. Low‐pressure gas adsorption experiments were conducted on the samples before and after extraction. The pore structure parameters were calculated from the gas adsorption data. The results show complex changes to the pore volumes and surface areas after extraction. The pore development of both the initial and extracted samples is strongly controlled by total organic carbon (TOC) content. Micropores developed mainly in organic matter (OM), while mesopores and macropores predominantly developed in fractions other than OM. The influence of EOM on micropores is stronger than on mesopores and macropores. Organic solvents with a higher boiling point should be used to explore the effect of EOM on pore structure in the future.     

Scale dependence of mineral dissolution rates within single pores and fractures

The possibility that gradients in concentration may develop within single pores and fractures, potentially giving rise to scale-dependent mineral dissolution rates, was investigated with experimentally validated reactive transport modeling. Three important subsurface mineral phases that dissolve at widely different rates, calcite, plagioclase, and iron hydroxide, were considered. Two models for analyzing mineral dissolution kinetics within a single pore were developed: (1) a Poiseuille Flow model that applies laboratory-measured dissolution kinetics at the pore or fracture wall and couples this to a rigorous treatment of both advective and diffusive transport within the pore, and (2) a Well-Mixed Reactor model that assumes complete mixing within the pore, while maintaining the same reactive surface area, average flow rate, geometry, and multicomponent chemistry as the Poiseuille Flow model. For the case of a single fracture, a 1D Plug Flow Reactor model was also considered to quantify the effects of longitudinal versus transverse mixing. Excellent agreement was obtained between results from the Poiseuille Flow model and microfluidic laboratory experiments in which pH 4 and 5 solutions were flowed through a single 500 μm diameter by 4000 μm long cylindrical pore in calcite. The numerical modeling and time scale analysis indicated that rate discrepancies arise primarily where concentration gradients develop under two necessary conditions: (1) comparable rates of reaction and advective transport, and (2) incomplete mixing via molecular diffusion. For plagioclase and iron hydroxide, the scaling effects are negligible at the single pore and fracture scale because of their slow rates. In the case of calcite, where dissolution rates are rapid, scaling effects can develop at high flow rates from 0.1 to 1000 cm/s and for fracture lengths less than 1 cm. Under more normal flow conditions where flow is usually slower than 0.001 cm/s, however, mixing via molecular diffusion is effective in homogenizing the concentration field, thus eliminating any discrepancies between the Poiseuille Flow and the Well-Mixed Reactor model. The analysis suggests that concentration gradients are unlikely to develop within single pores and fractures under typical geological/hydrologic conditions, implying that the discrepancy between laboratory and field rates must be attributed to other factors.     

Scaling of adsorption reactions: U(VI) experiments and modeling

Iron-coated sands were prepared via two common protocols, a precipitation method, where Fe was precipitated directly onto the sand in a single step, and an adsorption method, where pure goethite was prepared in the first step and then adsorbed onto the sand in a second step. The coated sands from both the systems were characterized using scanning electron microscopy, energy-dispersive spectroscopy, X-ray diffraction, and selective Fe extraction. Although neither of the methods produced a completely crystalline Fe coating, the precipitation method produced sands with larger portions of amorphous Fe than the adsorption method, with the fraction of amorphous Fe decreasing with increasing Fe content. Uranium(VI) adsorption isotherms and pH adsorption edges were measured on three coated sands with Fe contents ranging from 0.04% to 0.3%. Experimentally, the adsorption of U(VI) onto the three sands was more comparable when normalized to surface area than when normalized to Fe content. A surface complexation model, although originally developed for U(VI) adsorption onto amorphous Fe oxide, captured the differences in adsorption when adjusted for the surface area of the coated sand. The findings indicate that surface area is a better scaling parameter than Fe content in predicting U(VI) adsorption to Fe-dominated media. These findings are significant because many common surface complexation models are parameterized on the basis of Fe content rather than specific surface area. Although the interactions of U(VI) and Fe-coated sands were used as representative adsorbate and adsorbent, the general principles may be applicable to other adsorbate–adsorbent systems as well.     

Diagenesis of oxyanions (V, U, Re, and Mo) in pore waters and sediments from a continental margin

This research tests the hypothesis that trace metals respond to the extent of reducing conditions in a predictable way. We describe pore water and sediment measurements of iron (Fe), manganese (Mn), vanadium (V), uranium (U), rhenium (Re), and molybdenum (Mo) along a transect off Washington State (USA). Sediments become less reducing away from the continent, and the stations have a range of oxygen penetration depths (depth to unmeasurable O₂ concentration) varying from a few millimeters to five centimeters. When oxygen penetrates ∼1 cm or less, Fe is reduced in the pore waters but reoxidized near the sediment-water interface, preventing a flux of Fe²⁺ to overlying waters, whereas Mn oxides are reduced and Mn²⁺ diffuses to overlying waters. Both Re and U authigenically accumulate in sediments. Only at the most reducing location, where the oxygen penetrates 0.3 cm below the sediment-water interface, does the surface 30 cm of sediments become reducing enough to authigenically accumulate Mo.Stations in close proximity to the Juan de Fuca Ridge crest are enriched in Mn and Fe from hydrothermal plume processes. Both V and Mo clearly associate with Mn cycling, whereas U may be associating with either Mn oxides and/or Fe oxyhydroxides. Rhenium is uncomplicated by adsorption to Mn oxides and/or Fe oxyhydroxides, and Re accumulation in sediments appears to be due solely to the extent of reducing conditions. Therefore, authigenic sediment Re enrichment appears to be the best indicator for intermediate reducing conditions, where oxygen penetrates less than ∼1 cm below the sediment-water interface, when coupled with negligible authigenic Mo enrichment.     

Relative contributions of sulfate- and iron(III) reduction to organic matter mineralization and process controls in contrasting habitats of the Georgia saltmarsh

The objectives of this study were to partition out the predominant anaerobic respiration pathways coupled to C oxidation and to further elucidate the controls of anaerobic C respiration in three major saltmarsh habitats at Skidaway Island, GA; the short form of Spartina alterniflora (SS), the tall form of S. alterniflora (TS), and unvegetated, bioturbated creekbank (CB). Geochemical analysis of pore water and solid phase constituents revealed that the SS site experienced highly reducing conditions with two orders of magnitude higher pore water sulfide inventories (1.884 mmol m⁻²) than TS (0.003 mmol m⁻²) and CB (0.005 mmol m⁻²), respectively. Conversely, reactive Fe(III) inventories at TS (2208 mmol m⁻²) and CB (2881 mmol m⁻²) were up to 7–9 times higher than at SS (338 mmol m⁻²). Incubations and intact core experiments indicated that reduction accounted for 95% (SS), 37% (TS) and 66% (CB) of total anaerobic respiration. There was no detectable Fe(III) reduction at SS, while Fe(III) reduction accounted for up to 70% of C oxidation in the 3–6 cm depth interval at TS and 0–3 cm depth of CB, and on average, approximately 55% of C oxidation over two-thirds of marsh surface area. Laboratory manipulations provided further evidence for the importance of Fe(III) reduction as the accumulation rates of fermentation products were high when Fe(III) reduction was inhibited by removing the Fe(III) minerals from highly bioturbated CB sediments with higher Fe(III) mineral contents. Anaerobic C oxidation, - and Fe(III)-reduction rates appeared to be highest at the TS site during active plant growth in summer. Overall results suggest that bioturbation by macrofauna is the overriding factor in modulating the pathway of C mineralization in the saltmarsh, whereas availability of organic substrates from plants is a key factor in controlling the C oxidation rate.     

Analytical Artifacts Associated with the Chelating Resin Extraction of Dissolved Rare Earth Elements in Natural Water Samples

In order to determine rare earth elements (REE) in coastal seawater and groundwater samples using an inductively coupled plasma mass spectrometer, a time-efficient chelating resin column method has been widely used for small water volumes (<100 mL). We obtained improved, quantitative (>95%) results for extracting REE from most of the seawater (including the certified reference materials) and groundwater samples at extraction conditions of pH 5.8–6.0, flow rates <1.2 mL min⁻¹, and 1.2 g of wet resin weight (Chelex 100, Bio-Rad, 7 mm diameter). However, we often encountered large fractionations of HREE (heavy REE) relative to LREE (light REE) associated with chelating resin extraction for some organic-rich coastal seawater samples. This fractionation could be due to unidentified complexation of HREE with natural organic substances in water samples. Our results imply that many previous observations reporting the natural fractionation of HREE using this method could have been misleading. Thus, we suggest that the quantitative (>95%) extraction of REE should be confirmed by using either one of the HREE (i.e., Tm) as a spike or isotope dilution for natural aqueous samples which have large matrix effects.     

Characterization of dissolved organic matter in anoxic rock extracts and in situ pore water of the Opalinus Clay

Dissolved organic matter (DOM) from the Opalinus Clay, a potential host rock for the disposal of radioactive waste, was isolated under strictly anoxic conditions from ground rock material and compared with DOM of in situ pore water samples. For the extractions, deionized water, synthetic pore water (SPW, water containing all major ions at pore water concentrations but no organic matter) and 0.1 M NaOH were used. The influence of the solid-to-liquid ratio, extraction time, acid-pretreatment and O₂ exposure of the rock material on the isolated DOM were investigated. Liquid chromatography coupled with a total organic C detector (LC-OCD) and reverse-phase ion chromatography were used to characterize the DOM size distributions and to determine the low molecular weight organic acid (LMWOA) contents in the pore water samples and the rock extracts.The results revealed that only a small portion of the total organic C of the rock material (<0.38%) was extractable, even after removal of carbonates by acid-pretreatment. The concentrations of dissolved organic C (DOC) were found to range from 3.9 ± 0.4 to 8.0 ± 0.8 mg/L in the anoxic extracts. The pore waters exhibited similar DOC concentrations ranging from 1.2 to 15.8 ± 0.5 mg/L. The analysis by LC-OCD showed that the DOM extracted under anoxic conditions and the pore water DOM mainly consisted of hydrophilic compounds of less than 500 Da. The DOM extracted with SPW was most similar in size to the pore water DOM. Grinding the rock under oxic conditions increased the DOC yields and shifted the size distribution toward higher molecular weight compounds compared to the strictly anoxic treatment. Acetate, lactate and formate were identified in all extracts and in the pore water. In total, LMWOA accounted for 36% of the total DOC in both pore water and SPW extracts. The results imply that controlled anoxic conditions and the use of SPW as an extractant are required to isolate DOM from Opalinus Clay rocks which most resembles the in situ pore water DOM with respect to its size distribution and the LMWOA contents.     

Mercury mobility and bioavailability in soil from contaminated area

The mobility and bioavailability of mercury in the soil from the area near a plant using elemental mercury for manufacturing thermometers, areometers, glass energy switches and other articles made of technical glass has been evaluated. Mercury has been determined by sequential extraction method and with additional thermo desorption stage to determine elemental mercury. The procedure of sequential extraction involves five subsequent stages performed with the solutions of chloroform, deionized water, 0.5 M HCl, 0.2 M NaOH and aqua regia. The mean concentration of total mercury in soil was 147 ± 107 μg g⁻¹ dry mass (range 62–393), and the fractionation revealed that mercury was mainly bound to sulfides 56 ± 8% (range 45–66), one of the most biounavailable and immobile species of mercury in the environment. The fractions that brought lower contribution to the total mercury content were semi-mobile humic matter 22 ± 9% (range 11–34) and elemental mercury 17 ± 5% (range 8–23). The contributions brought by the highly mobile and toxic organomercury compounds were still lower 2.3 ± 2.7% (range 0.01–6.5). The lowest contributions brought the acid-soluble mercury 1.5 ± 1.3% (range 0.1–3.5) and water-soluble mercury 1.0 ± 0.3% (range 0.6–1.7). The surface layer of soil (0–20 cm) was characterized by higher mercury concentrations than that of the subsurface soil (60–80 cm), but the fractional contributions were comparable. The comparison of mercury fractionation results obtained in this study for highly polluted soils with results of fractionation of uncontaminated or moderately contaminated samples of soil and sediments had not shown significant statistical differences; however, in the last samples elemental mercury is usually present at very low concentrations. On the basis of obtained correlation coefficients it seems that elemental mercury soils from “Areometer” plant are contaminated; the main transformation is its vaporization to atmosphere and oxidation to divalent mercury, probably mainly mediated by organic matter, and next bound to humic matter and sulfides.     

Evaluation of diffuse and preferential flow pathways of infiltrated precipitation and irrigation using oxygen and hydrogen isotopes

Subsurface-water flow pathways in three different land-use areas (non-irrigated grassland, poplar forest, and irrigated arable land) in the central North China Plain were investigated using oxygen (¹⁸O) and hydrogen (²H) isotopes in samples of precipitation, soils, and groundwater. Soil water in the top 10 cm was significantly affected by both evaporation and infiltration. Water at 10–40 cm depth in the grassland and arable land, and 10–60 cm in poplar forest, showed a relatively short residence time, as a substantial proportion of antecedent soil water was mixed with a 92-mm storm infiltration event, whereas below those depths (down to 150 cm), depleted δ¹⁸O spikes suggested that some storm water bypassed the shallow soil layers. Significant differences, in soil-water content and δ¹⁸O values, within a small area, suggested that the proportion of immobile soil water and water flowing in subsurface pathways varies depending on local vegetation cover, soil characteristics and irrigation applications. Soil-water δ¹⁸O values revealed that preferential flow and diffuse flow coexist. Preferential flow was active within the root zone, independent of antecedent soil-water content, in both poplar forest and arable land, whereas diffuse flow was observed in grassland. The depleted δ¹⁸O spikes at 20–50 cm depth in the arable land suggested the infiltration of irrigation water during the dry season. Temporal isotopic variations in precipitation were subdued in the shallow groundwater, suggesting more complete mixing of different input waters in the unsaturated zone before reaching the shallow groundwater.

     

Spatial variation in pore water geochemistry in a mangrove system (Pai Matos island, Cananeia-Brazil)

Spatial variation in salinity, pH, redox potential, and in the concentrations of dissolved Mn, Fe²⁺ and sulphides in pore water were investigated in a mangrove system in the state of São Paulo (Brazil). Total organic C (TOC), S, Fe and Mn were analyzed in the solid phase, along with acid volatile sulphide (AVS), density of roots and percentage of sand. Five zones, situated along the length of a 180 m transect were considered in the study. Four of these were colonized by different species of vascular plants (Spartina, Laguncularia, Avicennia and Rhizophora) and were denominated soils; the other was not colonized by vegetation, and was denominated sediment. The results indicated important differences between the physicochemical conditions of the pore water in the vegetated zones and the sediment. In the former, two geochemical environments were identified, based on soil depths. The upper 20 cm contained the largest quantity of roots, and the conditions were oxic (Eh > 350 mV) or suboxic (Eh: 100–350 mV), acidic, and with high concentrations of Fe and Mn in the pore water. Below this depth, the soil became anoxic, the concentration of sulphides (HS⁻) increased significantly and the concentrations of dissolved Fe and Mn decreased significantly. The total S and the AVS fraction increased with depth, while TOC concentrations decreased, indicating that the decreases in Fe and Mn were due to the precipitation of metal sulphides. However, clear differences among the vegetated zones were not observed. The sediment was always anoxic, but with low concentrations of sulphide in the interstitial water, and was neutral or slightly alkaline. As in the soils, the concentrations of sulphides and total S increased significantly with depth, indicating that the conditions favoured the synthesis and stability of metal sulphides.