Applied Geochemistry (v.21, #9)

Cyclic base extraction is a commonly used method for the isolation of humic acids from soils and sediments. However, every extract may differ in chemical composition due to the complex nature of humic acids. To better understand the chemical composition of each extract, the heterogeneous property of humic acids and their speciation in environmental samples, eight fractions of humic acids were obtained in the present work by progressive base-extraction of Pahokee peat, and their chemical composition was characterized using two complementary pyrolytic techniques, namely conventional pyrolysis and methylation pyrolysis (TMAH) GC/MS. These quick and effective procedures provide an insight into the structure of macromolecules. The work shows that the lignin-derived aromatic compounds are major components of pyrolysates in both pyrolytic techniques, while aliphatic compounds originating from microorganisms and plants are minor components. Other compounds derived from proteins and carbohydrates at lower concentrations were also detected. Fatty acids were found in the pyrolysis without methylation, indicating their association with humic acid in a free state. These compounds are different from those formed during pyrolysis with in situ methylation, where fatty acids are generally believed to be the cleavage products of carboxylic groups bound to humic acids. A relative decreasing abundance of aromatic components and increasing abundance of aliphatic components in the pyrolysates as the peat was progressively extracted was also observed in this work, suggesting that the extraction of more hydrophobic aliphatics may be delayed in comparison to the aromatic components. Speciation and origin differences may also be important particularly considering that the contribution from lignin organic matter decreased with extraction number, as the contribution of microbial organic matter increased. The observed change in chemical composition with the extracted fractions indicates again that the humic acid distribution and their speciation are complex, and complete extractions are necessary to obtain a representative humic acid sample.

Kinetics of chromate reduction by pyrite and biotite under acidic conditions by Chul-Min Chon; Jae Gon Kim; Hi-Soo Moon (1469-1481).
The removal of chromate from aqueous solutions, using finely ground pyrite and biotite, was investigated by batch experiments. The kinetics and mechanism of chromate reduction are discussed here. Chromate reduction by pyrite was about 100 times faster than that by biotite, and was also faster at pH 3 than 4. When pyrite was used, more than 90% of the initial chromate was reduced within 4 h at pH 4, and within 40 min. at pH 3. However, with biotite more than 400 h was required for the reduction of 90% of the initial chromate. The results indicate that the rate of chromate reduction was strongly depending on the amount and dissolution rate of the Fe(II) in the minerals. The reduction of chromate at pH 4 resulted in the precipitation of (Cr, Fe)(OH)3(s), which is believed to have limited the concentrations of dissolved Cr(III) and Fe(III) to less than the expected values. When biotite was used, the amounts of decreased Fe(II) and reduced Cr(VI) showed no stoichiometric relationship, which implies that not only was there chromate reduction by Fe(II) ions in the acidic solution, but also heterogeneous reduction of Fe(III) ions by structural Fe(II) in biotite. However, the results from a series of the experiments using pyrite showed that the concentrations of the decreased Fe(II) and the reduced Cr(VI) were close to the stoichiometric ratio of 3:1. This was because the oxidation of pyrite rapidly created Fe(II) ions, even in oxygenated solutions, and the chromate reduction by the Fe(II) ions was significantly faster than the Fe(II) ion oxygenation. When compared with the experimental sets controlled at an initial pH of 3, the pH of the biotite batch, which was not controlled, increased to 3.4. Because of the increase in the pH, Cr(VI) was not completely removed, and 25% (1.2–1.3 mg/L Cr(VI)) of the initial concentration remained for up to 1000 h. The pH increase is, in most cases, caused by the hydrolysis of clay minerals. However, in the pyrite batches, there was no difference in the variations of the chromate reduction in relation to the pH control. There was also no difference in the capacity and rate of Cr(VI) reduction in 0.01 M NaCl or Na2SO4 solutions. In the 0.01 M NaH2PO4 solution pyrite experiment, the Cr(VI) was not completely removed, despite the maintenance of the pH at 3. The dominant Fe species was about 10 mg/L Fe(III) and few Fe(II) ions existed in solution. The Fe phosphate (Fe3(PO4)2 or FePO4) coatings on the surface of pyrite prevented access of O2 or Cr(VI). Therefore, the surface coatings are likely to have caused the deterioration of the Cr(VI) reduction capacity in the NaH2PO4 solution.

Population statistics for As concentrations in rocks, sediments and ground water differ by geology and land use features in the New England region, USA. Significant sources of As in the surficial environment include both natural weathering of rocks and anthropogenic sources such as arsenical pesticides that were commonly applied to apple, blueberry and potato crops during the first half of the 20th century in the region. The variation of As in bedrock ground water wells has a strong positive correlation with geologic features at the geologic province, lithology group, and bedrock map unit levels. The variation of As in bedrock ground water wells also has a positive correlation with elevated stream sediment and rock As chemistry. Elevated As concentrations in bedrock wells do not correlate with past agricultural areas that used arsenical pesticides on crops. Stream sediments, which integrate both natural and anthropogenic sources, have a strong positive correlation of As concentrations with rock chemistry, geologic provinces and ground water chemistry, and a weaker positive correlation with past agricultural land use. Although correlation is not sufficient to demonstrate cause-and-effect, the statistics favor rock-based As as the dominant regional source of the element in stream sediments and ground water in New England. The distribution of bedrock geology features at the geologic province, lithology group and map unit level closely correlate with areas of elevated As in ground water, stream sediments, and rocks.

A baseline determination of CO2 and CH4 fluxes and soil gas concentrations of CO2 and CH4 was made over the Teapot Dome oil field in the Naval Petroleum Reserve No. 3 (NPR-3) in Wyoming, USA. This was done in anticipation of experimentation with CO2 sequestration in the Pennsylvanian Tensleep Sandstone underlying the field at a depth of 1680 m.The baseline data were collected during the winter, 2004 in order to minimize near-surface biological activity in the soil profile. The baseline data were used to select anomalous locations that may be the result of seeping thermogenic gas, along with background locations. Five 10-m holes were drilled, 3 of which had anomalous gas microseepage, and 2 were characterized as “background.” These were equipped for nested gas sampling at depths of 10-, 5-, 3-, 2-, and 1-m depths. Methane concentrations as high as 170,000 ppmv (17%) were found, along with high concentrations of C2H6, C3H8, n-C4H10, and i-C4H10. Much smaller concentrations of C2H4 and C3H6 were observed indicating the beginning of hydrocarbon oxidation in the anomalous holes. The anomalous 10-m holes also had high concentrations of isotopically enriched CO2, indicating the oxidation of hydrocarbons. Concentrations of the gases decreased upward, as expected, indicating oxidation and transport into the atmosphere. The ancient source of the gases was confirmed by 14C determinations on CO2, with radiocarbon ages approaching 38 ka within 5 m of the surface.Modeling was used to analyze the distribution of hydrocarbons in the anomalous and background 10-m holes. Diffusion alone was not sufficient to account for the hydrocarbon concentration distributions, however the data could be fit with the addition of a consumptive reaction. First-order rate constants for methanotrophic oxidation were obtained by inverse modeling. High rates of oxidation were found, particularly near the surface in the anomalous 10-m holes, demonstrating the effectiveness of the process in the attenuation of CH4 microseepage. The results also demonstrate the importance of CH4 measurements in the planning of a monitoring and verification program for geological CO2 sequestration in sites with significant remaining hydrocarbons (i.e. spent oil reservoirs).

Factors controlling the chemical composition of water interacting with finely-crushed kimberlite have been investigated by sampling pore waters from processed kimberlite fines stored in a containment facility. Discharge water from the diamond recovery plant and surface water from the containment facility, which acts as plant intake water, were also sampled. All waters sampled are pH-neutral, enriched in SO4, Mg, Ca, and K, and low in Fe. Pore-water samples, representing the most concentrated waters, are characterized by the highest SO4 (up to 4080 mg l−1), Mg (up to 870 mg l−1), and Ca (up to 473 mg l−1). The water discharged from the processing plant has higher concentrations of all major dissolved constituents than the intake water. The dominant minerals present in the processed fines and the kimberlite ore are serpentine and olivine, with small amounts of Ca sulphate and Fe sulphide restricted to mud xenoclasts. Reaction and inverse modeling suggest that much of the water-rock interaction takes place within the plant and involves the dissolution of chrysotile and Ca sulphate, and precipitation of silica and Mg carbonate. Evapoconcentration also appears to be a significant process affecting pore water composition in the containment facility. The reaction proposed to be occurring during ore processing involves the dissolution of CO2(g) and may represent an opportunity to sequester atmospheric CO2 through mineral carbonation.

The biogeochemical behaviour of U(VI) in the simulated near-field of a low-level radioactive waste repository by James R. Fox; Robert J.G. Mortimer; Gavin Lear; Jonathan R. Lloyd; Ian Beadle; Katherine Morris (1539-1550).
Microbial processes have the potential to affect the mobility of radionuclides, including U in radioactive wastes. A range of geochemical, molecular biological and mineralogical techniques were applied to investigate stable element biogeochemistry and U solubility in the simulated “near-field” (or local environment) of a low-level radioactive waste (LLW) repository. The experiments used a microbial inoculum from the trench disposal area of the UK LLW repository at Drigg, Cumbria, England, in combination with a synthetic trench leachate representing the local environment at the Drigg site. In batch culture experiments in the absence of U, a classic redox progression of terminal electron accepting processes (TEAPs) occurred in the order NO 3 - , Fe(III) and SO 4 2 - reduction. When 126 μM U was added to the system as U(VI)aq, up to 80% was reduced to U(IV) by the indigenous microbial consortium. The U(IV) was retained in solution in these experiments, most likely by complexation with citrate present in the experimental medium. No U(VI)aq was reduced in sterile cultures, confirming that U(VI)aq reduction was microbially mediated. Interestingly, when U(VI)aq was present, the progression of TEAPs was altered. The rate of Fe(III) reduction slowed compared to experiments without U(VI)aq, and SO4 reduction occurred at the same time as U(VI) reduction. Finally, an experiment where SO 4 2 - -reducing microorgansisms were inhibited by Na molybdate showed no ingrowth of sulfide minerals, but U(VI) reduction continued in this experiment. This suggested that sulfide minerals did not play a significant role in abiotically reducing U(VI) in these systems, and that metal-reducing microorganisms were dominant in mediating U(VI) reduction. Bacteria closely related to microorganisms found in engineered and U-contaminated environments dominated in the experiments. Denaturing gradient gel electrophoresis (DGGE) on 16SrRNA products amplified from broad specificity primers showed that after incubation, differences in diversity and abundance of the microbial culture were observed between U and non-U experiments. These results indicate that the biogeochemistry of the LLW repository near-field stimulates reduction of U(VI)(aq) to U(IV) under anaerobic conditions and that the fate of reduced U(IV) will depend on the complexants present in LLW systems.

CO2 emissions and heat flow through soil, fumaroles, and steam heated mud pools at the Reykjanes geothermal area, SW Iceland by Thráinn Fridriksson; Bjarni Reyr Kristjánsson; Halldór Ármannsson; Eygerður Margrétardóttir; Snjólaug Ólafsdóttir; Giovanni Chiodini (1551-1569).
Carbon dioxide emissions and heat flow through soil, steam vents and fractures, and steam heated mud pools were determined in the Reykjanes geothermal area, SW Iceland. Soil diffuse degassing of CO2 was quantified by soil flux measurements on a 600 m by 375 m rectangular grid using a portable closed chamber soil flux meter and the resulting data were analyzed by both a graphical statistical method and sequential Gaussian simulations. The soil temperature was measured in each node of the grid and used to evaluate the heat flow. The heat flow data were also analyzed by sequential Gaussian simulations. Heat flow from steam vents and fractures was determined by quantifying the amount of steam emitted from the vents by direct measurements of steam flow rate. The heat loss from the steam heated mud pools was determined by quantifying the rate of heat loss from the pools by evaporation, convection, and radiation. The steam flow rate into the pools was calculated from the observed heat loss from the pools, assuming that steam flow was the only mechanism of heat transport into the pool. The CO2 emissions from the steam vents and mud pools were determined by multiplying the steam flow rate from the respective sources by the representative CO2 concentration of steam in the Reykjanes area. The observed rates of CO2 emissions through soil, steam vents, and steam heated mud pools amounted to 13.5 ± 1.7, 0.23 ± 0.05, and 0.13 ± 0.03 tons per day, respectively. The heat flow through soil, steam vents, and mud pools was 16.9 ± 1.4, 2.2 ± 0.4, and 1.2  ± 0.1 MW, respectively. Heat loss from the geothermal reservoir, inferred from the CO2 emissions through the soil amounts to 130 ± 16 MW of thermal energy. The discrepancy between the observed heat loss and the heat loss inferred from the CO2 emissions is attributed to steam condensation in the subsurface due to interactions with cold ground water. These results demonstrate that soil diffuse degassing can be a more reliable proxy for heat loss from geothermal systems than soil temperatures. The soil diffuse degassing at Reykjanes appears to be strongly controlled by the local tectonics. The observed diffuse degassing defines 3–5 elongated N–S trending zones (000–020°). The orientation of the diffuse degassing structures at Reykjanes is consistent with reported trends of right lateral strike slip faults in the area. The natural CO2 emissions from Reykjanes under the current low-production conditions are about 16% of the expected emissions from a 100 MWe power plant, which has recently been commissioned at Reykjanes.

Hydrochemical evidence of the depth of penetration of anthropogenic recharge in sandstone aquifers underlying two mature cities in the UK by R.G. Taylor; A.A. Cronin; D.N. Lerner; J.H. Tellam; S.H. Bottrell; J. Rueedi; M.H. Barrett (1570-1592).
Pollution of urban groundwater is routinely reported but the profile of contamination with depth in urban aquifers is rarely resolved. This limits understanding of the depth of penetration of urban recharge and contaminants, and use of urban groundwater. Penetration of anthropogenic solutes (major ions, trace metals) in Permo-Triassic sandstone aquifers underlying two mature conurbations in the UK was investigated through depth-specific, groundwater sampling of dedicated multilevel piezometers. Identification of solute origin and biogeochemical processes (e.g. denitrification, mineral dissolution) was aided by use of stable isotope ratios (34S/32S, 18O/16O, 15N/14N, 13C/12C) and chemical speciation modelling (PHREEQC). Depth profiles of aquifer hydrochemistry reveal penetration of anthropogenic solutes to depths of between 30 and 47 m below ground in the unconfined sandstone and confirm the contributions of faecal and industrial effluents to urban recharge. They also highlight the complexity of solute loading and difficulty resolving solute origin from the range of potential sources in urban groundwater. Faecally-derived NO3 is the most pervasive contaminant exceeding drinking-water quality guidelines and is associated with elevated concentrations of B and SO4. Elevated concentrations of Li, B, Cr and Co are observed at depth in groundwater contaminated by long-term industrial land use (metalworking). Observed penetration of anthropogenic solutes in the unconfined sandstone is consistent with post-development recharge of urban groundwater (residence times <230 a) indicated by flow modelling, and suggests tentatively that urban abstraction to depths of up to 50 m below ground in the unconfined Permo-Triassic sandstone is required to scavenge contaminated groundwater.

Sediments, mosses and algae, collected from lake catchments of the Larsemann Hills, East Antarctica, were analysed to establish baseline levels of trace metals (Ag, As, Cd, Co, Cr, Cu, Ni, Sb, Pb, Se, V and Zn), and to quantify the extent of trace metal pollution in the area. Both impacted and non-impacted sites were included in the study. Four different leaching solutions (1 M MgCl2, 1 M CH3COONH4, 1 M NH4NO3, and 0.3 N HCl) were tested on the fine fraction (<63 μm) of the sediments to extract the mobile fraction of trace metals derived from human impact and from weathering of basement lithologies. Results of these tests indicate that dilute HCl partly dissolves primary minerals present in the sediment, thus leading to an overestimate of the mobile trace metal fraction. Concentrations of trace metals released using the other 3 procedures indicate negligible levels of anthropogenic contribution to the trace metal budget. Data derived from this study and a thorough characterisation of the site allowed the authors to define natural baseline levels of trace metals in sediments, mosses and algae, and their spatial variability across the area. The results show that, with a few notable exceptions, human activities at the research stations have contributed negligible levels (lower than natural variability) of trace metals to the Larsemann Hills ecosystem. This study further demonstrates that anthropogenic sources of trace metals can be correctly identified and quantified only if natural baselines, their variability, and processes controlling the mobility of trace metals in the ecosystem, have been fully characterised.

Metal and arsenic distribution in soil particle sizes relevant to soil ingestion by children by Karin Ljung; Olle Selinus; Erasmus Otabbong; Marika Berglund (1613-1624).
Ingestion of soil is a common behaviour in young children as a means of exploring their surroundings. Much attention has been given to remediation of point-source polluted sites with regard to potential health risks for children. However, because of diffuse pollution and long-range atmospheric deposition, soil contaminant levels are generally increased in urban areas compared to their rural counterparts, even in areas located away from any point sources of pollution. Intake of urban soil can thereby result in significant amounts of the child’s daily metal intake. In the present study, soil samples were collected from 25 playgrounds around urban Uppsala, Sweden and analysed for contents of Al, As, Fe, Cr, Cu, Cd, Hg, Mn, Ni, Pb, W and Zn. Prior to aqua regia digestion, the samples were wet-sieved in order to separate soil particle fractions representing deliberate (<4 mm) and involuntary (<50 μm) soil ingestion by children, as well as a third size fraction of 50–100 μm representing soil that is easily transported by suspension. While the metal and As contents in the 50–100 μm fraction were similar to those of the <4 mm fraction, the <50 μm fraction had metal and As contents on average one and a half times higher than those of the <4 mm fraction. The metal and As contents correlated negatively with the sand content in both particle size fractions <4 mm and 50–100 μm, suggesting a general decrease in metal and As content with increasing sand content. However, a positive correlation was found between sand content and the metal and As contents of the finest fraction (<50 μm), suggesting that when the sand content is high, the bulk of the sorbed elements are on the finest particles. The difference between metal and As contents in the different size fractions was greater in the soil sample with the highest sand content than in the sample with the lowest sand content. This implies that texture is a significant factor in metal and As distribution in soils with moderate metal and As contents, when the number of binding sites associated with small particles is low. Tolerable daily intake (TDI) values for Pb and As were exceeded at all sites, and at two sites for Cd, for children with pica behaviour. A high ingestion rate of mainly small particles could also result in the TDI value for Pb being exceeded at 10 sites and that for As at one site. This study also found that soil analysis by the procedure recommended by Swedish authorities accurately represents the metal intake from deliberate soil ingestion, whereas involuntary soil ingestion of mainly small particles could result in metal intakes which are up to twice as high.