Applied Geochemistry (v.21, #12)

Stable isotope evidence for the atmospheric origin of CO2 involved in carbonation of MSWI bottom ash by C. Fléhoc; J.-P. Girard; P. Piantone; F. Bodénan (2037-2048).
Stable isotopes were used to constrain the origin of CO2 involved in the ageing process of municipal solid waste incineration (MSWI) bottom ash under open-air conditions. The δ13C and δ18O values of CaCO3 occurring in MSWI bottom ash samples of variable age and the δ13C of the residual organic matter content were measured, and laboratory assessments made of the isotopic fractionation accompanying CaCO3 neo-formation during accelerated carbonation experiments of bottom ash or pure lime with atmospheric or industrial CO2. The results indicate that stable isotopic compositions exhibited by fresh and aged bottom ash samples reflect non-equilibrium processes resembling those described in the carbonation of concrete and mortar. They also lead to conclusions on the prevalent involvement of atmospheric CO2 in the open-air carbonation of MSWI bottom ash.

Cancrinite and sodalite formation in the presence of cesium, potassium, magnesium, calcium and strontium in Hanford tank waste simulants by Youjun Deng; Markus Flury; James B. Harsh; Andrew R. Felmy; Odeta Qafoku (2049-2063).
High-level radioactive tank waste solutions that have leaked into the subsurface at the US Department of Energy Hanford Site, Washington, are chemically complex. Here, the effect of five cations, Cs+, K+, Sr2+, Ca2+ and Mg2+, on mineral formation and transformation pathways under conditions mimicking Hanford tank leaks is investigated. Sodium silicate was used to represent the dissolved silicate from sediments. The silicate was added into a series of simulants that contained 0.5 M aluminate, 1 M or 16 M NaOH, and the NO 3 - salts of the cations. The precipitates were monitored by X-ray diffraction, scanning electron microscopy, and X-ray energy dispersive spectroscopy. In the 1 M NaOH simulants, low concentration of Cs+ (<100 mM) did not affect the formation of lepispheric cancrinite and sodalite, whereas only highly crystalline cancrinite formed when Cs+ concentration was ⩾250 mM. An unidentified feldspathoid or zeolite intermediate phase was observed in the presence of high concentrations of Cs+ (500 mM). The presence of K+ did not alter, but slowed, the formation of cancrinite and sodalite. The presence of divalent cations led to the formation of metastable or stable silicates, aluminates, hydroxides, or aluminosilicates. The formation of these intermediate phases slowed the formation of cancrinite and sodalite by consuming OH, silicate, or aluminate. Compared with the concentrations used in this study, the concentrations of radioactive Cs+ and Sr2+ in the tank solutions are much lower and divalent cations (Ca2+ and Mg2+) released from sediments likely precipitate out as hydroxides, silicates or aluminates; therefore, the authors do not expect that the presence of these monovalent and divalent cations significantly affect the formation of cancrinite and sodalite in the sediments underneath the leaking waste tanks.

Mineralogical and geochemical patterns of urban surface soils, the example of Pforzheim, Germany by Stefan Norra; Mahesh Lanka-Panditha; Utz Kramar; Doris Stüben (2064-2081).
This study presents a combined geochemical and mineralogical survey of urban surface soils. Many studies on urban soils are restricted to purely chemical surveys in order to investigate soil pollution caused by anthropogenic activities such as traffic, heating, industrial processing, waste disposal and many more. In environmental studies, chemical elements are often distinguished as lithogenic and anthropogenic elements. As a novel contribution to those studies, the authors combined the analysis of a broad set of chemical elements with the analysis of the main mineralogical phases. The semi-quantification of mineralogical phases supported the assignment of groups of chemical elements to lithogenic or anthropogenic origin. Minerals are important sinks for toxic elements. Thus, knowledge about their distribution in soils is crucial for the assessment of the environmental hazards due to pollution of urban soils. In Pforzheim, surface soils (0–5 cm depth) from various land use types (forest, agriculture, urban green space, settlement areas of various site densities) overlying different geological units (clastic and chemical sediments) were investigated. Urban surface soils of Pforzheim reflect to a considerable degree the mineral and chemical composition of parent rocks. Irrespective of the parent rocks, elevated concentrations of heavy metals (Zn, Cu, Pb, Sn, Ag) were found in soils throughout the whole inner urban settlement area of Pforzheim indicating pollution. These pollutants will tend to accumulate in inner urban surface soils according to the available adsorption capacity, which is normally higher in soils overlying limestone than in soils overlying sandstone. However, inner urban surface soils overlying sandstone show elevated concentrations of carbonates, phyllo-silicates and Fe and elevated pH values compared with forest soils overlying sandstone. Thus, in comparison to forest soils overlying sandstones, inner urban soils overlying sandstone affected by pollution concurrently possess elevated concentrations of mineral phases typically providing relatively high adsorption capacities for heavy metals.

Here the authors present results of an isotope study on precipitation collected during a 2-a period from a rain-gauge network consisting of 6 stations located at different elevations in the Hyblean Mountains (HM) region, in south-eastern Sicily. The slope of the local meteoric water line (δD  = 6.50 δ 18O + 9.87) obtained for the region suggests that precipitation is affected by evaporation during rainfall events. The main variations in rainwater isotope composition are due to seasonal effects and elevation. An average 2H excess value of +21.2‰ was found for precipitation events less affected by evaporation (i.e. when the rainfall was >65 mm/month). The spatial distribution of O isotope composition of precipitation shows a negative gradient from east and south to the inner areas. The depositional rate of Cl, used as a tracer of the origin of air masses, is highest at the coastal rain-gauges (SR and MRG stations) and lowest on the northern flank of the HM region (SC station). Based on these findings, a model is proposed for the origin of precipitation in the HM region, which assumes that a Mediterranean-derived component is the main source of moisture in the studied area. D/H and 18O/16O ratios of inferred meteoric recharge waters were also compared with the isotope composition of waters collected from the main local springs and wells. The best linear fit of the δ 18O vs δD relationship for Hyblean groundwater is δD  = 4.85 δ 18O–2.01. The enrichment of heavy isotopes in Hyblean groundwater is probably due to evaporation occurring after precipitation events or to a recharging contribution from surface waters (lakes or rivers) enriched in heavy isotopes.

Comparison of soil solution chemistry sampled by centrifugation, two types of suction lysimeters and zero-tension lysimeters by Christine E. Geibe; Rolf Danielsson; Patrick A.W. van Hees; Ulla S. Lundström (2096-2111).
The choice of sampling method for soil solution is of great importance. In this paper soil solution chemistry sampled by centrifugation, two types of suction lysimeters and zero-tension lysimeters have been studied with the purpose of investigating systematic differences between them. The samples were taken at 4 depths from an acidified forest soil as well as from adjacent lime and ash treated soils. A centrifugation drainage method was compared with two types of suction lysimeters (‘Rhizon’ and ‘Prenart’) and zero-tension lysimeters. About half of the 27 variables measured showed a significant difference between the sampling methods used. Typically the centrifuged samples had lower pH (4.0 vs. 4.4), Ca (21 μM vs. 30 μM) and Mg (25 μM vs. 34 μM) concentrations and higher Cl (330 μM vs. 230 μM) and DOC (4.4 mM vs. 3.2 mM) concentrations than the Rhizon lysimeters. Also the other lysimeters showed significant differences compared to the centrifuged samples for about half the number of analytes. Centrifuged samples had higher concentrations of all analytes except NO3 and PO4 compared to zero-tension lysimeters and also for all analytes except NO3 and Al compared to Prenart lysimeters. Among the environmental factors considered depth showed an influence to some extent, while sampling occasion had a great significant impact on the difference between the centrifugation method and the Rhizon lysimeters. Factors like individual pits or soil treatment did not show any influence on the difference between the methods.

A field filtration method for the concentration and separation of suspended particulate matter (SPM) from freshwater systems and the subsequent determination of minor, trace and ultra trace elements (As, Ba, Be, Cd, Co, Cr, Cs, Cu, Ga, Hf, Mo, Nb, Ni, Pb, Rb, Sb, Sc, Sn, Sr, Ta, Th, Tl, U, V, W, Zn and Zr) is validated with respect to detection limits, precision and bias. The validation comprises the whole procedure including filtration, sample digestion and instrumental analysis. The method includes two digestion procedures (microwave acid digestion and alkali fusion) in combination with inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma quadrupole mass spectrometry (ICP-QMS). Total concentrations of these 27 trace and minor elements have been determined in suspended particulate matter (SPM) from lake and river water with low levels of suspended solids (<2 mg L−1  DW), and a wide range of element concentrations. The precision of the method including filtration, digestion and instrumental determination ranges between 8% and 18% RSD for most elements on a dry weight basis. Higher recovery after acid digestion is found for some elements, probably because of volatilization or retention losses in the fusion procedure. Other elements show higher recovery after fusion, which is explained by more efficient decomposition of refractory mineral phases relative to the non-total acid digestion. Non-detectable concentrations of some elements are reported due to small differences between blank filter levels and the amounts of elements present on the filters after sampling. The method limits of detection range between 0.7 ng and 2.65 μg, as estimated from the blank filter samples. These detection limits are 10–550 times higher compared to the corresponding instrumental limits of detection. The accuracy and bias of the overall analytical procedure was assessed from replicate analysis of certified reference materials. A critical evaluation of the instrumental capabilities of the ICP-QMS instrumentation in comparison with a double focusing sector field plasma mass spectrometry technique (ICP-SFMS) is also included. It was found that a modified microwave acid digestion procedure in combination with ICP-SFMS could replace ICP-AES determinations and fusion digestions for most of the investigated elements. Guidelines and limitations for this time- and labour- efficient procedure, offering accurate results for the majority of elements studied are discussed.

Mineral soil horizons (Ae, Bhf1, Bhf2, Bf, BC and C) were carefully collected from two podzolic soil profiles in the Lake Clair watershed (Québec) in order to assess anthropogenic trace metal accumulation. Petrographic and selective analyses were performed to establish the soil mineralogy and properties. Furthermore, a complete sequential extraction procedure has been applied to help understanding the complex chemical speciation of Pb in forest soils. Chemical speciation of Pb showed a strong vertical gradient: 85% of this metal is mainly partitioned in refractory minerals in the C-horizon whereas in the upper Bhf1 and Ae-horizons, less than 50% of Pb is associated with this fraction. In the Ae-horizon, for example, 35%, 30% and 12% of total Pb, respectively, is associated with the exchangeable, labile organic matter and amorphous Fe-Mn oxides fractions. The distribution of Pb and Cr in the studied forest soils mainly reflects progressive contamination of the watershed by anthropogenic atmospheric sources. The anthropogenic source is indicated by elevated Cr and Pb concentrations in the topsoil (Bhf and Ae) horizons and by strong negative correlation between 206Pb/207Pb ratios and total Pb concentrations. According to these isotopic values, penetration of anthropogenic Pb does not exceed 10 cm in both soil profiles. Below this depth, both Pb concentrations and isotopic ratios remain nearly constant and similar to values observed in pre-anthropogenic sediments from Lake Clair. These values are interpreted as the natural geochemical backgrounds of the watershed. Based on that behaviour, calculated anthropogenic Pb net inputs amounted to between 1.24 and 1.8 g/m2.

Groundwater recharge history and hydrogeochemical evolution in the Minqin Basin, North West China by W.M. Edmunds; Jinzhu Ma; W. Aeschbach-Hertig; R. Kipfer; D.P.F. Darbyshire (2148-2170).
The Minqin Basin is a type area for examining stress on groundwater resources in the Gobi Desert, and has been investigated here using a combination of isotopic, noble gas and chemical indicators. The basin is composed of clastic sediments of widely differing grain size and during the past half century over 10 000 boreholes have been drilled with a groundwater decline of around 1 m a−1. Modern diffuse recharge is unlikely to exceed 3 mm a−1, as determined using unsaturated zone profiles and Cl mass balance. A small component of modern (<50 a) groundwater is identified in parts of the basin from 3H–3He data, probably from irrigation returns. A clear distinction is found between modern waters with median δ 18O values of 6.5 ± 0.5‰ and most groundwaters in the basin with more depleted isotopic signatures. Radiocarbon values as pmc range from 0.6% to 85% modern, but it is difficult to assign absolute ages to these, although a value of 20% modern C probably represents the late Pleistocene to Holocene transition. The δ 13C compositions remain near-constant throughout the basin (median value of −8.1‰δ 13C) and indicate that carbonate reactions are unimportant and also that little reaction takes place. There is a smooth decrease in 14C activity accompanied by a parallel increase in 4He accumulations from S–N across the basin, which define the occurrence of a regional flow system. Noble gas temperatures indicate recharge temperatures of about 5.6 °C for late Pleistocene samples, which is some 2–3 °C cooler than the modern mean annual air temperature and the recharge temperature obtained from several Holocene samples. Groundwaters in the Minqin Basin have salinities generally below 1 g/L and are aerobic, containing low Fe but elevated concentrations of U, Cr and Se (mean values of 27.5, 5.8 and 5.3 μg L−1, respectively). Nitrate is present at baseline concentrations of around 2 mg L−1 but there is little evidence of impact of high NO3 from irrigation returns. Strontium isotope and major ion ratios suggest that silicate reactions predominate in the aquifer. The results have important implications for groundwater management in the Minqin and other water-stressed basins in NW China – a region so far destined for rapid development. The large proportion of the water being used at present is in effect being mined and significant changes are urgently needed in water use strategy.

Spatial variation in pore water geochemistry in a mangrove system (Pai Matos island, Cananeia-Brazil) by X.L. Otero; T.O. Ferreira; P. Vidal-Torrado; F. Macías (2171-2186).
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.

Phosphate-induced metal stabilization involving the reactive medium Apatite II™ [Ca10−x Na x (PO4)6−x (CO3) x (OH)2], where x  < 1, was used in a subsurface permeable reactive barrier (PRB) to treat acid mine drainage in a shallow alluvial groundwater containing elevated concentrations of Zn, Pb, Cd, Cu, SO4 and NO3. The groundwater is treated in situ before it enters the East Fork of Ninemile Creek, a tributary to the Coeur d’Alene River, Idaho. Microbially mediated SO4 reduction and the subsequent precipitation of sphalerite [ZnS] is the primary mechanism occurring for immobilization of Zn and Cd. Precipitation of pyromorphite [Pb10(PO4)6(OH,Cl)2] is the most likely mechanism for immobilization of Pb. Precipitation is occurring directly on the original Apatite II. The emplaced PRB has been operating successfully since January of 2001, and has reduced the concentrations of Cd and Pb to below detection (2 μg L−1), has reduced Zn to near background in this region (about 100 μg L−1), and has reduced SO4 by between 100 and 200 mg L−1 and NO3 to below detection (50 μg L−1). The PRB, filled with 90 tonnes of Apatite II, has removed about 4550 kg of Zn, 91 kg of Pb and 45 kg of Cd, but 90% of the immobilization is occurring in the first 20% of the barrier, wherein the reactive media now contain up to 25 wt% Zn. Field observations indicate that about 30% of the Apatite II material is spent (consumed).