The average molecular weight and shape of the “polymeric acids” found in Black Trona Water from the Green River Basin

Macromolecular organic material, called “polymeric acids”, has been isolated from Black Trona Water by exhaustive dialysis and characterized as the sodium salt in 0.10 M sodium carbonate, pH 10, by several physico-chemical methods. Analysis by gel filtration chromatography on Sepharose-CL 6B indicates that the “polymeric acids” are polydisperse and composed of species of relatively high molecular weight ( 4 × 10⁵, using proteins as standards). With this method, the range of molecular weights appears to be rather narrow. If “polymeric acids” are transferred from sodium carbonate, pH 10, into distilled water, selfassociation occurs and all species elute in the void volume. The weight-average molecular weight determined in 0.10 M sodium carbonate, pH 10, by the light scattering method is 1.7 × 10⁵. Sedimentation velocity analysis at 20°C with the analytical ultracentrifuge gives a value for S_20,w of 5.4 and the shape of the Schlieren patterns suggest a polydisperse sample with a relatively narrow range of sizes. Analysis of the molecular weight distribution by a sedimentation equilibrium method indicates that the range of molecular weights is 8 × 10⁴ to 2.1 × 10⁵. The partial specific volume ( ) of “polymeric acids” is 0.874 ml/g. Viscosity measurements yield a value for [η] of 2.5 ml/g, which indicates that the “polymeric acids” are compact (spherical or ellipsoidal) in shape.     

The role of supergene sulphuric acid during weathering in small river catchments in low mountain ranges of Central Europe: Implications for calculating the atmospheric CO2 budget

The geochemistry of dissolved and suspended loads in river catchments of two low mountain ranges in Central Europe allows comparison of pertinent chemical weathering rates. Distinct differences in lithology, i.e. granites prevailing in the Black Forest compared to Palaeozoic sediments in the Rhenish Massif, provide the possibility to examine the influence of lithology on weathering. Here we determine the origin of river water using the stable isotope ratio δ¹⁸O_H2O and we quantify the geogenic proportions of sulphate from stable isotope ratios δ³⁴S_SO4 and δ¹⁸O_SO4. Particularly in catchments with abundant pyrite, determination of the geogenic amount of sulphate is important, since oxidation of pyrite leads to acidity, which increases weathering. Our results show that spatially averaged silicate weathering rates are higher for the river catchments Acher and Gutach in the Black Forest (10–12 t/km²/yr) compared to the river catchments of the Möhne dam and the Aabach dam in the Rhenish Massif (2–6 t/km²/yr). Correspondingly, the CO₂ consumption by silicate weathering in the Black Forest (334–395 × 10³ mol/km²/yr) is more than twice as high as in the Rhenish Massif (28–151 × 10³ mol/km²/yr). These higher rates for watersheds of the Black Forest are likely due to steeper slopes leading to higher mechanical erosion with respective higher amounts of fresh unweathered rock particulates and due to the fact that the sediments in the Rhenish Massif have already passed through at least one erosion cycle. Carbonate weathering rates vary between 12 and 38 t/km²/yr in the catchments of the Rhenish Massif. The contribution of sulphuric acid to the silicate weathering is higher in the catchments of the Rhenish Massif (9–16%) than in the catchments of the Black Forest (5–7%) due to abundant pyrite in the sediments of the Rhenish Massif. Three times higher long-term erosion rates derived from cosmogenic nuclides compared to short-term erosion rates derived from river loads in Central Europe point to three times higher CO₂ consumption during the past 10³ to 10⁴ years.     

Micro-FTIR spectroscopy of liptinite macerals in coal

Reflectance FTIR microspectroscopy has been used to investigate the chemical structure of the liptinite macerals, alginite, bituminite, sporinite, cutinite and resinite in bituminous coals of Carboniferous to Tertiary age. In comparison with the spectra of vitrinite in the same coals, the micro-FTIR spectra of liptinite macerals are characterized by stronger aliphatic CH_x absorptions at 3000–2800 and 1460–1450 cm⁻¹, less intense aromatic C=C ring stretching vibration and aromatic CH out of plane deformation at 1610–1560 and 900–700 cm⁻¹ respectively and various intense acid C=O group absorptions at 1740–1700 cm⁻¹. The peaks at 1000–900 cm⁻¹ due to aliphatic CH₂ wagging vibrations in olefins and at 730–720 cm⁻¹ due to CH₂ rocking vibration in long chain aliphatic substances ([CH₂]_n, n≥4), are characteristic of liptinite macerals. Collectively the micro-FTIR spectral characteristics indicate that liptinite is composed of greater numbers of long chain aliphatics, fewer aromatics and a broader range of oxygen-containing groups than other macerals. Marked differences exist in micro-FTIR spectra within the liptinite maceral group. Alginite has the strongest aliphatic and least aromatic absorptions followed by bituminite, resinite, cutinite and sporinite. The aliphatic components in alginite are the longest chained and least branched whereas those in sporinite are the shortest chained and most branched. Bituminite, resinite and cutinite are intermediate. Notable differences in micro-FTIR spectra of individual liptinite macerals, such as intensities and peak locations of aromatic C=C in alginite, C=O groups in bituminite and resinite and substituted aromatic CH and C–O–C groups in cutinite and sporinite, also exist, which are attributed to differences in depositional environments or biotaxonomy.     

Origin and formation pathways of kerogen-like organic matter in recent sediments off the Danube delta (northwestern Black Sea)

The chemical structure, source(s), and formation pathway(s) of kerogen-like organic matter (KL) were investigated in recent sediments from the northwestern Black Sea, off the Danube delta. Three sections from a sediment core collected at the mouth of the Sulina branch of the delta, under an oxic water column, were examined: S₀ (0–0.5 cm bsf), S₁₀ (10–13 cm bsf), and S₂₀ (20–25 cm bsf). The bulk geochemical features of these sediments (total organic carbon, organic C/N atomic ratio, δ¹³C_org) were determined. Thereafter, KL was isolated from the samples, as the insoluble residue obtained after HF/HCl treatment. KL chemical composition was investigated via spectroscopic (FTIR, solid state ¹³C and ¹⁵N NMR) and pyrolytic (Curie point pyrolysis–gas chromatography–mass spectrometry) methods, and the morphological features were examined by scanning and transmission electron microscopy. Similar morphological features and chemical composition were observed for the three KLs and they suggested that the selective preservation of land-plant derived material as well as of resistant aliphatic biomacromolecules (probably derived from cell walls of freshwater microalgae) was the main process involved in KL formation. Besides, some melanoidin-type macromolecules (formed via the degradation-recondensation of products mainly derived from proteinaceous material) and/or some encapsulated proteins also contributed to the KL chemical structure.     

Freshwater and Atlantic water inflows to the deep northern Barents and Kara seas since ca 13 C ka: : foraminifera and stable isotopes

Foraminiferal stable isotopes and assemblages from Franz Victoria and St. Anna troughs provide a valuable record of freshwater and Atlantic Water flows to the northern Barents and Kara seas from deglaciation to present. The δ¹⁸O and δ¹³C of planktonic Neogloboquadrina pachyderma (s) and benthic Elphidium excavatum were up to 1.4‰ lower than present at ca 13, 11.5, and 10 ¹⁴C ka (global sea-level corrected), mostly reflecting substantial freshwater inputs coincident with glacial–marine sediment deposition. Cassidulina teretis exceeded 40% of benthic foraminifera ca 13 and 10 ¹⁴C ka, indicating subsurface penetrations of Atlantic Water. The transition to postglacial marine conditions is marked by a 1‰ rise in foraminiferal δ¹⁸O and a sharp fall in % C. teretis soon after 10 ¹⁴C ka. These changes imply reduced inputs of freshwater and Atlantic Water. Subsequent isotopic and foraminiferal assemblage variations reflect changing Atlantic Water conditions “upstream” in the Nordic Seas and shifts between the warm Fram Strait and cold Barents Sea branches of Atlantic Water. We hypothesize that glacial-isostatically induced deepening by up to 150 m influenced Atlantic Water inflows to the northern Barents Sea during deglaciation and the Holocene. Thus, effects of isostatic recovery have to be factored into paleoceanographic reconstructions.     

Chemistry of rainwaters in the south Pacific area of Russia

On the south-eastern edge of Russia, the chemical composition of rainwater is controlled by sea salts, terrestrial material, as well as volcanic (Kuril islands volcanic area) and anthropogenic emissions, mostly in the southern part of the area. The predominant major ions of the Primorye, Sakhalin and the Kuril Islands rainwaters were respectively HCO₃⁻–SO₄²⁻, Ca–Na, and of Cl–Na. Concentration of trace elements changes within 1–2 orders of magnitude but some difference in the distribution of the elements between continental and island rainwater is found. The concentration of the chemical elements in the particulate fraction varies from < 10% to 90% of the total concentration (dissolved + particulate) with the following distribution: Tl, Na, Ca, Sr, Zn, Cd (< 10%)–Be, Th, Bi, Rb, U, K, Sc (10–20%)–Cu, Mn, Mg, Mo, Se, Ba, Ni, As, Ag, Cs, Co, Y, Ga, V (20–50%)–Sb, Pb, Ge, Cr, Fe, Al (50–90%).The concentration of elements of the particulate fraction of the rainwater usually is significantly different from concentrations in the crust, including both higher and lower concentrations. The terrestrial contribution to dissolved elements was evaluated and follows the decreasing order: Fe > K, Mg, Ca > Ba, Sr > Na (65–1%). Close order was found for total (dissolved and solid) concentrations. Sea salt contribution to dissolved element concentration in the rainwater decrease in the following order: Cl, Mg > K, SO₄ > Ca > HCO₃⁻, Ba, Fe (78–0.1%). Calculation of anthropogenic and volcanic inputs for two ions (Cl⁻ and SO₄²⁻) shows that anthropogenic inputs for the Vladivostok and Yuzno-Sakhalinsk cities can be evaluated as 15–20% of Cl⁻ and up to 80–90% of SO₄²⁻. Volcanic components in the Kuril Islands, where anthropogenic inputs are absent, can reach up to 76% of SO₄²⁻ and 36% of Cl⁻.     

Flow of river water into a karstic limestone aquifer—2. Dating the young fraction in groundwater mixtures in the Upper Floridan aquifer near Valdosta, Georgia

Tritium/helium-3 (³H/³He) and chlorofluorocarbon (CFCs, CFC–11, CFC–12, CFC–113) data are used to date the young fraction in groundwater mixtures from a karstic limestone aquifer near Valdosta, Georgia, where regional paleowater in the Upper Floridan aquifer receives recharge from two young sources—the flow of Withlacoochee River water through sinkholes in the river bed, and leakage of infiltration water through post-Eocene semi-confining beds above the Upper Floridan aquifer. In dating the young fraction of mixtures using CFCs, it is necessary to reconstruct the CFC concentration that was in the young fraction prior to mixing. The ³H/³He age is independent of the extent of dilution with older (³H-free and ³He_trit-free) water. The groundwater mixtures are designated as Type-1 for mixtures of regional paleowater and regional infiltration water and Type-2 for mixtures containing more than approximately 4% of river water. The fractions of regional paleowater, regional infiltration water, and Withlacoochee River water in the groundwater mixtures were determined from Cl⁻ and δ¹⁸O data for water from the Upper Floridan aquifer at Valdosta, Georgia.The chlorofluorocarbons CFC–11 and CFC–113 are removed by microbial degradation and/or sorption processes in most anaerobic (Type-2) groundwater at Valdosta, but are present in some aerobic Type-1 water. CFC–12 persists in both SO₄-reducing and methanogenic water. The very low detection limits for CFCs (approximately 0.3 pg kg⁻¹) permitted CFC–11 and CFC–12 dating of the fraction of regional infiltration water in Type-1 mixtures, and CFC-12 dating of the river-water fraction in Type-2 mixtures. Overall, approximately 50% of the 85 water samples obtained from the Upper Floridan aquifer have CFC–12-based ages of the young fraction that are consistent with the ³H concentration of the groundwater. Because of uncertainties associated with very low ³H and ³He content in dilute mixtures, ³H/³He dating is limited to the river-water fraction in Type-2 mixtures containing more than about 10% river water. Of the 41 water samples measured for ³H/³He dating, dilution of ³H and low ³He concentration limited ³H/³He dating to 16 mixtures in which ³H/³He ages are defined with errors ranging from ±2 to ±7.5 a (1 σ). After correction for dilution with (assumed) CFC-free regional infiltration water and regional paleowater in the Upper Floridan aquifer, adjusted CFC–12 ages agree with ³H/³He ages within 5 a or less in 7 of the 9 co-dated Type-2 mixtures.Tritium data and dating based on both CFC–11 and CFC–12 in Type-1 mixtures indicate that travel times of infiltration water through the overlying Post-Eocene semi-confining beds exceed 35 a. The CFC and ³H/³He dating indicate that the river fraction in most groundwater entered the groundwater reservoir in the past 20 to 30 a. Few domestic and municipal supply wells sampled intercept water younger than 5 a. Calculated velocities of river water in the Upper Floridan aquifer downgradient of the sinkhole area range from 0.4 to 8.2 m/d. Radiocarbon data indicate that ages of the regional paleowater are on the 10 000-a time scale. An average lag time of approximately 10 to 25 a is determined for discharge of groundwater from the surficial and intermediate aquifers above the Upper Floridan aquifer to the Withlacoochee River.     

Integrated hydrochemical method of water quality assessment for irrigation in arid areas: application to the Jilh aquifer, Saudi Arabia

Water samples from 72 wells tapping the Jilh aquifer were collected and analyzed for 10 different water quality parameters. Using these data, a regional irrigation water quality was assessed using three techniques: (i) United States Department of Agriculture method (USDA), (ii) Food and Agriculture Organization (FAO) guidelines for water quality assessment, and (iii) Water-Types approach. The USDA method revealed that the aquifer water salinity, as represented by electrical conductivity, EC_w, ranges from high salinity (C3: EC_w > 0.75–2.25 dS/m) to a very high salinity (C4: EC_w > 2.25 dS/m). The sodium adsorption ratio (SAR) varied from low (S1) to very high (S4) sodicity. Therefore, the water of the Jilh aquifer is dominantly of the C4–S2 class representing 56% of the total wells followed by C4–S1, C4–S3, C3–S1 and C4–S4 classes at 19%, 14%, 8%, and 3% of the wells respectively. The FAO system indicated moderate to severe restriction on the use for irrigation and slight to moderate ion toxicities for Na⁺, Cl⁻, B⁺, NO₃⁻ and HCO₃⁻. It is clear that, both USDA and FAO systems condemn the Jilh groundwater as hazardous for irrigation due to its high salt content, unless certain measures for salinity control are undertaken. The dominant salt constituents in the water are Mg–Cl₂, Na–Cl and Ca–Cl₂ as per the Water-Types method. However, due to the complexity in classifying the aquifer groundwater for irrigation, a simplified approach acknowledging three class groups (I-suitable water, II-conditionally suitable water and III-unsuitable water) adopted from the three methods, is suggested in this paper. The simplified approach combines C–S classes of the USDA method among these three groups according to the lowest ratings. The salinity of the FAO method has been split arbitrarily into slight and moderate subclasses with values of 0.7–2.25 and >2.25 dS/m, respectively; to match with the C3-class of the USDA system. The Water-Types were classified assuming that Ca–Cl₂ is the least hazardous salt, followed by Mg–Cl₂ and Na–Cl. Using this integrated hydrochemical method, the majority of the wells (92%) contain unsuitable water for irrigation (Group III) while the remaining wells (8%) are in Group II with water considered conditionally suitable for irrigation.     

U–Pb ages of Neoarchean granitoids from the Black Hills, South Dakota, USA: implications for crustal evolution in the Archean Wyoming province

Zircons in basement rocks from the eastern Wyoming province (Black Hills, South Dakota, USA) have been analyzed by ion microprobe (SHRIMP) in order to determine precise ages of Archean tectonomagmatic events. In the northern Black Hills (NBH) near Nemo, Phanerozoic and Proterozoic (meta)sedimentary rocks are nonconformably underlain by Archean biotite–feldspar gneiss (BFG) and Little Elk gneissic granite (LEG), both of which intrude older schists. The Archean granitoid gneisses exhibit a pervasive NW–SE-trending fabric, whereas an earlier NE–SW-trending fabric occurs sporadically only in the BFG, which is intruded by the somewhat younger LEG. Zircon crystals obtained from the LEG and BFG exhibit double terminations, oscillatory zoning, and Th/U ratios of 0.6±0.3—thereby confirming a magmatic origin for both lithologies. In situ analysis of the most U–Pb concordant domains yields equivalent ²⁰⁷Pb/²⁰⁶Pb ages (upper intercept, U–Pb concordia) of 2559±6 and 2563±6 Ma (both ±2σ) for the LEG and BFG, respectively, which constrains a late Neoarchean age for sequential pulses of magmatism in the NBH. Unzoned (in BSE) patches of 2560 Ma zircon commonly truncate coeval zonation in the same crystals with no change in Th/U ratio, suggesting that deuteric, fluid-assisted recrystallization accompanied post-magmatic cooling. A xenocrystic core of magmatic zircon observed in one LEG zircon yields a concordant age of 2894±6 Ma (±2σ). This xenocryst represents the oldest crustal material reported thus far in the Black Hills. Whether this older zircon originated as unmelted residue of 2900 Ma crust that potentially underlies the Black Hills or as detritus derived from 2900 Ma crustal sources in the Wyoming province cannot be discerned. In the southern Black Hills (SBH), the peraluminous granite at Bear Mountain (BMG) of previously unknown age intrudes biotite–plagioclase schist. Zircon crystals from the BMG are highly metamict and altered, but locally preserve small domains suitable for in situ analysis. A U–Pb concordia upper intercept age of 2596±11 Ma (±2σ) obtained for zircon confirms both the late Neoarchean magmatic age of the BMG and a minimum age for the schist it intrudes. Taken together, these data indicate that the Neoarchean basement granitoids were emplaced at 2590–2600 Ma (SBH) and 2560 Ma (NBH), most likely in response to subduction associated with plate convergence (final assembly of supercontinent Kenorland?). In contrast, thin rims present on some LEG–BFG zircons exhibit strong U–Pb discordance, high common Pb, and low Th/U ratios—suggesting growth or modification under hydrothermal conditions, as previously suggested for similar zircons from SE Wyoming. The LEG–BFG zircon rims yield a nominal upper intercept date of 1940–2180 Ma, which may represent a composite of multiple rifting events known to have affected the Nemo area between 2480 and 1960 Ma. Together, these observations confirm the existence of a Paleoproterozoic rift margin along the easternmost Wyoming craton. Moreover, the 2480–1960 Ma time frame inferred for rifting in the Black Hills (Nemo area) corresponds closely to a 2450–2100 Ma time frame previously inferred for the fragmentation of supercontinent Kenorland.     

Study on the kinetics of iron oxide leaching by oxalic acid

The presence of iron oxides in clay or silica raw materials is detrimental to the manufacturing of high quality ceramics. Although iron has been traditionally removed by physical mineral processing, acid washing has been tested as it is more effective, especially for extremely low iron (of less than 0.1% w/w). However, inorganic acids such as sulphuric or hydrochloric acids easily contaminate the clay products with SO₄²⁻ and Cl⁻, and therefore should be avoided as much as possible. On the other hand, if oxalic acid is used, any acid left behind will be destroyed during the firing of the ceramic products. The characteristics of dissolution of iron oxides were therefore investigated in this study.The dissolution of iron oxides in oxalic acid was found to be very slow at temperatures within the range 25–60 °C, but its rate increases rapidly above 90 °C. The dissolution rate also increases with increasing oxalate concentration at the constant pH values set within the optimum range of pH2.5–3.0. At this optimum pH, the dissolution of fine pure hematite (Fe₂O₃) (105–140 μm) follows a diffusion-controlled shrinking core model. The rate expression expressed as 1 − (2 / 3)x − (1 − x)^2 / 3 where x is a fraction of iron dissolution was found to be proportional to [oxalate]^1.5.The addition of magnetite to the leach liquor at 10% w/w hematite was found to enhance the dissolution rate dramatically. Such addition of magnetite allows coarser hematite in the range 0.5–1.4 mm to be leached at a reasonable rate.     

Geochemistry of metal-rich brines from central Mississippi Salt Dome basin, U.S.A.

Oil-field brines are the most favored ore-forming solutions for the sediment-hosted Mississippi Valley-type ore deposits. Detailed inorganic and organic chemical and isotope analyses of water and gas samples from six oil fields in central Mississippi, one of the very few areas with high metal brines, were conducted to study the inorganic and organic complexes responsible for the high concentrations of these metals. The samples were obtained from production zones consisting of sandstone and limestone that range in depth from 1900 to 4000 m (70–120°C) and in age from Late Cretaceous to Late Jurassic. Results show that the waters are dominantly bittern brines related to the Louann Salt. The brines have extremely high salinities that range from 160,000 to 320,000 mg/l total dissolved solids and are NaCaCl-type waters with very high concentrations of Ca (up to 48,000 mg/l) and other alkaline-earth metals, but with low concentrations of aliphatic acid anions. The concentrations of metals in many water samples are very high, reaching values of 70 mg/l for Pb, 245 mg/l for Zn, 465 mg/l for Fe and 210 mg/l for Mn. The samples with high metal contents have extremely low concentrations (<0.02 mg/l) of H₂S. Samples obtained from the Smackover Formation (limestone) have low metal contents that are more typical of oil-field waters, but have very high concentrations (up to 85 mg/l) of H₂S. Computations with the geochemical code SOLMINEQ.87 give the following results: (1) both Pb and Zn are present predominantly as aqueous chloride complexes (mainly as PbCl₄²⁻ and ZnCl₄²⁻, respectively); (2) the concentrations of metals complexed with short-chained aliphatic acid anions and reduced S species are minor; (3) organic acid anions are important in controlling the concentrations of metals because they affect the pH and buffer capacity of the waters at subsurface conditions; and (4) galena and sphalerite solubilities control the concentrations of Pb and Zn in these waters.     

Distribution of copper, zinc, lead and cadmium concentrations in stream sediments from the Mapocho River in Santiago, Chile

The Mapocho river, which crosses downtown Santiago, is one of the most important rivers in contact with a population of about six million inhabitants. Anthropogenic activities, industrialization, farming activities, transport, urbanization, animal and human excretions, domestic wastes and copper mining have affected the river, contaminating it and its sediments with heavy metals. Concentration and distribution of Cu, Zn, Pb and Cd were studied with the purpose of determining their bioavailability and their relation with the characteristics of the sediments. Freshly deposited seasonal sediments were collected from 0–8 cm depths from 6 locations (S₁ to S₆) along the 30-km long channel length, in the four seasons of year on the following dates: May 2001 (D₁, autumn); August 2001 (D₂, winter); October 2001 (D₃, spring) and January 2002 (D₄, summer). The dried samples were sifted to obtain the < 63-μm sediment fraction, since it has been shown that large amounts of heavy metals are bound in the fine-grained fraction of the sediment. Cu and Zn were analyzed by atomic absorption spectrophotometry and Pb and Cd by square wave anodic stripping voltammetry. The highest concentrations of Cu (2850 μg g^− 1) were found in the northern part of the river (S₁, average D₁–D₄), near the mountains and a copper mine, and then decreased downstream to 209 μg g^− 1 (S₆). Total Zn showed an irregular variation, with higher values at S₁ (1290 μg g^− 1) and high values in some winter sampling (1384 μg g^− 1 S₄, S₅–D₂). Pb showed different trends, increasing from S₁ to S₆ (17 to 61 μg g^− 1), with the highest values in the summer samples (83 μg g^− 1, S₄–S₆, D₄), and total Cd increased slightly from mean values of 0.2 and 0.5 μg g^− 1. Partition into five fractions was made using Tessier's analytical sequential extraction technique; the residue was treated with aqua regia for recovery studies, although this step is not part of the Tessier procedure. The results show that Cu, Zn and Pb in the sediments were dependent on the sampling places along the river, and variation in two years was low (D₁–D₄). The highest values of total organic matter, carbonate and conductivity were found in S₆, which has the smallest size particles, while at S₁ the sediments were predominantly sand and contain larger amounts of silica. Cu associated with carbonate decreased gradually from 58% (1771 μg g^− 1, S₁) to 16% (32 μg g^− 1, S₆); Cu bonded to reducible fraction was almost constant (33% to 37%), and Cu associated with oxidizable fraction increased from 7% (S₁) to 34% (S₆), but copper content was lower (214 to 68 μg g^− 1). Zn had a similar fractionation profile. However, Pb bound to oxidizable fraction did not show significant percent variation along the river (20% to 19%), but the amount bounded was 4 to 12 μg g^− 1. The residual fraction increased from 24% to 41% (5 to 25 μg g^− 1, S₁ to S₆). The distribution of Cd in the sediment was almost independent of the sampling stations and was bound to carbonate, reducible and residual fraction in similar proportion. Cu and Zn at S₁ were mainly bound to carbonates and reducible phases with 91% and 73% (2779 and 965 μg g^− 1, respectively), and with a change in the pH and/or the redox potential of the sediment–water system, these contaminants could easily enter the food chain. In S₆ the amount of Cu and Zn in these phases was 50% and 53% (100 to 313 μg g^− 1, respectively).     

The structure of Termination II (penultimate deglaciation and Eemian) in the North Atlantic

A study of the 140–100 ka interval in core T90-9P from the North Atlantic (45° N, 25° W), based on analysis of oxygen and carbon isotope records from planktonic and benthonic foraminifera, and from the bulk sediment fine fraction facilitates a detailed paleoceanographic reconstruction of the penultimate deglaciation (Termination II), and of the Eemian interglacial (δ¹⁸O stage 5e). The first step of Termination II was characterised by low productivity and a mixed water column, which was a remnant of glacial conditions. A 3 ka period of relatively stable conditions, with a stratified water column (‘Termination II pause’), occurred half-way through Termination II, and preceeded a second and more rapid climatic shift. The end of the deglaciation (Eemian maximum, i.e. isotopic event 5.53) initiated the establishment of strong, seasonal, water column stratification. North Atlantic Deep Water (NADW) production remained low during the complete glacial–interglacial transition. After the Eemian maximum, NADW prodution was restored, and bottom waters remained quite stable during the course of the Eemian, while surface waters gradually cooled in the second half of the stage. A short surface water cooling event accompanied by a reduced seasonal water column stratification and nutrient instability occurred at approximately 117 ka BP.     

Origin and composition of organic matter in tidal flat sediments from the German Wadden Sea

Two sediment cores of up to 550 cm length from an intertidal flat of the German Wadden Sea near the island of Spiekeroog were investigated for the quantity and composition of fossil organic matter (OM). The lowermost parts of the cores are dominated by grey mud of a salt marsh facies containing mainly terrestrial OM estimated to account for 60–75% of the total OM, based on δ¹³C values and the ratio of short to long chain n-alkanols. The terrigenous origin of the dominant fraction is indicated, among others, by high proportions of C₂₉ sterols and long chain n-alkanes typical of plant waxes. Coarse shell beds overlying the grey mud at 2–2.5 m depth represent a flooding and erosion event possibly related to heavy storm floods in the Middle Ages. Within the intertidal sand-dominated sediments in the upper parts of the cores total organic carbon (TOC) contents are generally low, ranging from 0.1% to 0.5%, and correlate well with the amount of mud fraction (r² 0.90). At the surface, marine OM has not undergone intense diagenetic alteration and so is the dominant fraction. Eroded peat particles are common throughout most of the sequence and values of the Phragmites peat indicator (PPI) > 5 indicate an origin from reed peat due to a high relative abundance of the n-C₂₄ alkane. Changes in the composition of microbial communities over the depth interval investigated are documented by varying compositions of unsaturated fatty acids with 16 and 18 carbons. Eicosapentaenoic acid (EPA) was detected along the entire cores and indicates the presence of EPA-producing bacterial strains.     

Primary fluid inclusions in galena crystals. II. Chemical composition of the liquid and gas phase

The chemical composition of primary individual inclusions in large galena crystals from the Madan ore district, Bulgaria (see Pt. I), is studied in this paper. The liquid phase was analysed for Na, K, Ca, Fe, Mn, Mg, NH _inf4 ^sup+ , Pb, Cu, Zn, Al, Cl^–, F^–, SO ₄ ^2– , HCO ₃ ^– , and HS^– (+S^2–): pH was also determined. The following analytical methods were used: atomic-absorption spectrophotometry, emission spectral analysis, spectrophotometry, nephelometry, microcrystalloscopic and drop reactions. The gas phase was mass-spectrometrically analysed after opening the vacuoles in vacuum. It was found to consist of water vapour and CO₂ only. It was also found that the solutions are chloride-sodium-potassium with a total salinity of 4–4.5%. They do not contain measurable amounts of sulphur components. The CO₂/H₂O ratios vary strongly between the various vacuoles, which is explained by the crystallization in boiling solutions. The problems of the hermeticity of inclusions, the partial pressure of CO₂, the temperature of crystallization, and of the possible role of boiling in the ore-forming process are discussed.     

Analysis of modern and fossil plant cuticles by Curie point Py-GC and Curie point Py-GC-MS: Recognition of a new, highly aliphatic and resistant biopolymer

This paper investigates to what extent the chemical constituents of plant cuticles (waxes and cutin) can survive diagenesis. Recent and fossil plant cuticles were analyzed by means of Curie point pyrolysis-gas chromatography and Curie point pyrolysis-gas chromatography-mass spectrometry. Recent cuticles were analyzed without treatment, after solvent extraction and after cutin depolymerization. Extensive series of straight-chain alkanes, alk-1-enes and α,ω)-alkadienes dominate the pyrolysates, especially after removal of the wax and cutin. ¹³C-NMR spectroscopy of the residue after removal of the cutin confirmed the presence of a new, highly aliphatic biopolymer and a polysaccharide fraction.The abundance of straight-chain alkanes, alk-1-enes and α,ω-alkadienes in the fossil plant cuticles indicates the chemical resistence of the biopolymer to diagenesis and may explain the occurrence of straight-chain aliphatic moieties in organic-matter-rich sediments and coals as revealed by “C-NMR spectroscopy and flash pyrolysis methods. The highly aliphatic biopolymer may function as an important oil precursor.     

Mechanism of the water and carbon dioxide solubility in oxides and silicates and the role of O−

The dissolution of water does not stop at the OH^– stage but may proceed further towards H₂ plus O^– formation. The discovery of atomic carbon dissolved in minerals suggests that, if CO₂ enters oxides and silicates at high pressures and temperatures, not only [CO₃]^2– ions but also [CO ₄ ^. ]^4– complexes are formed via a charge transfer which produces O^– and essentially zero-valent, atomic carbon. Under P —T-conditions of the mantle, where the solubility for water and CO₂ is high, the silicate phases formed may therefore consist to a large volume fraction of O^– ions which are much smaller than O^2–ions and strongly cova-lently bonding. The implications for the crystal chemistry of high pressure phases, for the petrology of mantle rocks are outlined.     

Hydrochemical and isotopic characteristics of groundwater in the Souss Upstream Basin, southwestern Morocco

Heterogeneous shallow Plio-Quaternary formations of the Souss Plain represent the most important aquifer in southern High Atlas Mountains in Morocco. The present work was conducted in the Souss Upstream Basin to identify the chemical characteristics and the origin of groundwater in an aquifer under semi-arid climate. Isotopic and hydrochemical compositions combined with geological and hydrogeological data were used for this purpose. The total dissolved solids vary from 239 to 997 mg l⁻¹, and the following groundwater types are recognized: Ca²⁺–Mg²⁺–HCO₃⁻, Ca²⁺–Mg²⁺–SO₄²⁻ and Ca²⁺–Mg²⁺–Cl⁻. The groundwater is saturated and slightly supersaturated with respect to carbonate minerals and undersaturated with respect to evaporite minerals, which means that the groundwater composition is largely controlled by the dissolution of carbonate rocks known in the basin. The isotopic contents of groundwaters ranged from −8‰ to −5.2‰ for δ¹⁸O, from −52‰ to −34‰ for δD, and from 0 to 5.5 TU for tritium. The hydrogen (δD) and oxygen (δ¹⁸O) isotope signatures reveal a significant infiltration before evaporation takes place, indicating a major recharge directly from fractures in the crystalline and limestone formations of Atlas Mountains (above 800 m a.s.l.) and infiltration of surface water in the alluvial cones at the border of the Atlas basins. The very low tritium values suggest that the groundwater recharge follows a long flow path and a mixing between old and modern water is shown. However, a slight evaporation effect is noted in the southern part of the basin close to the Anti-Atlas Mountains.     

Elucidation of different forms of organic carbon in marine sediments from the Atlantic coast of Spain using thermal analysis coupled to isotope ratio and quadrupole mass spectrometry

Analysis of river, estuary and marine sediments from the Atlantic coast of Spain using thermogravimetry–differential scanning calorimetry–quadrupole mass spectrometry–isotope ratio mass spectrometry (TG–DSC–QMS–IRMS) was used to (a) distinguish bulk chemical hosts for C within a sediment and humic acid fraction, (b) track C pools with differing natural C isotope ratios and (c) observe variation with distance from the coast. This is the first application of such a novel method to the characterisation of organic matter from marine sediments and their corresponding humic acid fractions. Using thermal analysis, a labile, a recalcitrant and a refractory carbon pool can be distinguished. Extracted humic fractions are mainly of recalcitrant nature. The proportion of refractory carbon is greatest in marine sediments and humic acid fractions. Quadrupole mass spectrometry confirmed that the greatest proportion of m/z 44 (CO₂) and m/z 18 (H₂O) were detected at temperatures associated with recalcitrant carbon (510–540 °C). Isotope analysis detected progressive enrichment in δ¹³C for the sediment samples with an increase in marine influence. Isotopic heterogeneity in the refractory organic matter in marine sediments could be due to products of anthropogenic origin or natural combustion products. Isotope homogeneity of humic acids confirms the presence of terrigenous C in marine sediments, allowing the terrestrial input to be characterised.     

Major ion chemistry of groundwaters in the Bahar area, Hamadan, western Iran

Hydrochemical investigations were carried out in Bahar area, Hamadan, western Iran, to assess the chemical composition of groundwater. The area falls in a semi-arid type of climate. In this area, groundwater has been exploited over the past century mainly for irrigation and water supply. A total of 135 representative groundwater samples were collected from different wells to monitor the water chemistry of various ions. Chemical analysis of the groundwater shows that the mean concentration of the cations is of the order Ca²⁺>Mg ²⁺>Na⁺>K⁺, while that for anions is SO₄^2–>HCO₃^–>Cl^–>NO₃^–. Statistical analyses indicate positive correlation between the following pairs of parameters Cl^– and Mg ²⁺ (r=0.71), Cl^– and Na⁺ (r=0.76), HCO₃^– and Na⁺ (r=0.56), SO₄^2– and Mg²⁺ (r=0.76), SO₄^2– and Na⁺ (r=0.69). Water presents a large spatial variability of the chemical facies (Ca-HCO₃, Ca-SO₄, Mg-HCO₃, Mg-SO₄, Na-HCO₃) which is in relation to their interaction with the geological formations of the basin (carbonates, dolomite and various silicates) and evaporation. The hydrochemical types Ca-HCO₃ and Ca-SO₄ dominate the largest part of the studied area. The dissolution of halite, calcite, dolomite, and gypsum explains part of the contained Na ⁺, Ca²⁺, Mg²⁺, Cl^–, SO₄^2– and HCO₃^–, but other processes, such as cation exchange and weathering of aluminosilicates also contribute to the water composition.