New operational method of testing colloid complexation with metals in natural waters

A dialysis procedure was used to assess the distribution coefficients of ∼50 major and trace elements (TEs) between colloidal (1 kDa–0.22 μm) and truly dissolved (<1 kDa) phases in Fe- and organic-rich boreal surface waters. These measurements allowed quantification of both TE partitioning coefficients and the proportion of colloidal forms as a function of solution pH (from 3 to 8). Two groups of elements can be distinguished according to their behaviour during dialysis: (i) elements which are strongly associated with colloids and exhibit significant increases of relative proportion of colloidal forms with pH increase (Al, Ba, Cd, Co, Cr, Cu, Fe, Ga, Hf, Mn, Ni, Pb, rare earth elements (REEs), Sr, Th, U, Y, Zn, Zr and dissolved organic C) and (ii) elements that are weakly associated with colloids and whose distribution coefficients between colloidal and truly dissolved phases are not significantly affected by solution pH (As, B, Ca, Cs, Ge, K, Li, Mg, Mo, Na, Nb, Rb, Sb, Si, Sn, Ti, V). Element speciation was assessed using the Visual MINTEQ computer code with an implemented NICA-Donnan humic ion binding model and database. The model reproduces quantitatively the pH-dependence of colloidal form proportion for alkaline-earth (Ba, Ca, Mg, Sr) and most divalent metals (Co, Cd, Mn, Ni, Pb, Zn) implying that the complexation of these metals with low molecular weight organic matter (<1 kDa fraction) is negligible. In contrast, model prediction of colloidal proportion (fraction of 1 kDa–0.22 μm) of Cu²⁺ and all trivalent and tetravalent metals is much higher than that measured in the experiment. This difference may be explained by (i) the presence of strong metal-binding organic ligands in the <1 kDa fraction whose stability constants are several orders of magnitude higher than those of colloidal humic and fulvic acids and/or (ii) coprecipitation of TE with Fe(Al) oxy(hydr)oxides in the colloidal fraction, whose dissolution and aggregation controls the pH-dependent pattern of TE partitioning. Quantitative modeling of metal – organic ligand complexation and empirical distribution coefficients corroborate the existence of two colloidal pools, formerly reported in boreal surface waters: “classic” fulvic or humic acids binding divalent transition metals and alkaline-earth elements and large-size organo-ferric colloids transporting insoluble trivalent and tetravalent elements.     

Carbon mass-balance modelling and carbon isotope exchange processes in dynamic caves

Diverse interpretations have been made of carbon isotope time series in speleothems, reflecting multiple potential controls. Here we study the dynamics of ¹³C and ¹²C cycling in a particularly well-constrained site to improve our understanding of processes affecting speleothem δ¹³C values. The small, tubular Grotta di Ernesto cave (NE Italy) hosts annually-laminated speleothem archives of climatic and environmental changes. Temperature, air pressure, pCO₂, dissolved inorganic carbon (DIC) and their C isotopic compositions were monitored for up to five years in soil water and gas, cave dripwater and cave air. Mass-balance models were constructed for CO₂ concentrations and tested against the carbon isotope data. Air advection forces winter pCO₂ to drop in the cave air to ca. 500 ppm from a summer peak of ca. 1500 ppm, with a rate of air exchange between cave and free atmosphere of approximately 0.4 days. The process of cave ventilation forces degassing of CO₂ from the dripwater, prior to any calcite precipitation onto the stalagmites. This phase of degassing causes kinetic isotope fractionation, i.e. ¹³C-enrichment of dripwater whose δ¹³C_DIC values are already higher (by about 1‰) than those of soil water due to dissolution of the carbonate rock. A subsequent systematic shift to even higher δ¹³C values, from −11.5‰ in the cave drips to about −8‰ calculated for the solution film on top of stalagmites, is related to degassing on the stalagmite top and equilibration with the cave air. Mass-balance modelling of C fluxes reveals that a very small percentage of isotopically depleted cave air CO₂ evolves from the first phase of dripwater degassing, and shifts the winter cave air composition toward slightly more depleted values than those calculated for equilibrium. The systematic ¹³C-enrichment from the soil to the stalagmites at Grotta di Ernesto is independent of drip rate, and forced by the difference in pCO₂ between cave water and cave air. This implies that speleothem δ¹³C values may not be simply interpreted either in terms of hydrology or soil processes.     

High-resolution profiles of trace metals assessed by DGT techniques in lake sediment porewaters

The technique of diffusive gradients in thin films (DGT) was applied to obtain high-resolution vertical profiles of trace metals in sediment porewater of a eutrophic lake, Lake Chaohu. All sampling sediments were under anaerobic conditions with Eh values below 0, the redox potential profile in M4 was relatively stable, and higher Eh values in M4 than that in M1 were observed due to hydrodynamic effects. Fe, Mn and As exhibited closely corresponding profiles due to the co-release of Fe and Mn oxides and the reduction of As. Higher Fe and Mn concentrations and lower As concentrations were observed in M1 of the western half-lake than those in M4 of the eastern half-lake due to different sources and metal contamination levels in the two regions. Cu and Zn showed increasing concentrations similar to Mn and Fe at 1–2 cm depth of sediments, while DGT measured Co, Ni, Cd and Pb concentrations decreased down to 3–4 cm in the profiles. Co, Ni, Cu, Zn, Cd and Pb showed insignificant regional concentration variances in the western and eastern half-lakes. According to the R(C _DGT/C _{centrifugation}) values, the rank order of metal labilities decrease as follows: Fe (>1) > Cu, Pb, Zn (>0.9) > Co, Ni, Cd (>0.3) > Mn, As (>0.1).     

Magnesium-isotope fractionation during low-Mg calcite precipitation in a limestone cave - Field study and experiments

The chemical and isotopic composition of speleothem calcite and particularly that of stalagmites and flowstones is increasingly exploited as an archive of past environmental change in continental settings. Despite intensive research, including modelling and novel approaches, speleothem data remain difficult to interpret. A possible way foreword is to apply a multi-proxy approach including non-conventional isotope systems. For the first time, we here present a complete analytical dataset of magnesium isotopes (δ²⁶Mg) from a monitored cave in NW Germany (Bunker Cave). The data set includes δ²⁶Mg values of loess-derived soil above the cave (−1.0 ± 0.5‰), soil water (−1.2 ± 0.5‰), the carbonate hostrock (−3.8 ± 0.5‰), dripwater in the cave (−1.8 ± 0.2‰), speleothem low-Mg calcite (stalactites, stalagmites; −4.3 ± 0.6‰), cave loam (−0.6 ± 0.1‰) and runoff water (−1.8 ± 0.1‰) in the cave, respectively. Magnesium-isotope fractionation processes during weathering and interaction between soil cover, hostrock and solute-bearing soil water are non-trivial and depend on a number of variables including solution residence times, dissolution rates, adsorption effects and potential neo-formation of solids in the regolith and the carbonate aquifer. Apparent Mg-isotope fractionation between dripwater and speleothem low-Mg calcite is about 1000lnα_Mg-cc-Mg(aq) = −2.4‰. A similar Mg-isotope fractionation (1000lnα_Mg-cc-Mg(aq) ≈ −2.1‰) is obtained by abiogenic precipitation experiments carried out at aqueous Mg/Ca ratios and temperatures close to cave conditions. Accordingly, ²⁶Mg discrimination during low-Mg calcite formation in caves is highly related to inorganic fractionation effects, which may comprise dehydration of Mg²⁺ prior to incorporation into calcite, surface entrapment of light isotopes and reaction kinetics. Relevance of kinetics is supported by a significant negative correlation of Mg-isotope fractionation with the precipitation rate for inorganic precipitation experiments.     

Adsorption and surface complexation modeling of palladium,rhodium and platinum in surficial semi-arid soils and sediment

Sorption isotherms, time-dependent adsorption and surface complexation modeling studies were used to investigate the post-depositional mobility of three of the platinum group-elements (Pd, Rh, and Pt) in semi-arid soil and sediment samples with varying surface properties. The acidity constants (Log K_a1 and Log K_a2), optimized from batch titration data, ranged from 4.69 to 5.34 for Log K_a1 and from −6.51 to −7.61 for Log K_a2, suggesting the occurrence of both protonation and deprotonation reactions on the solid surfaces. Partition coefficients and removal rates of the metals had a general trend of Pd > Pt > Rh. The sediment sample, with the highest clay content and exchangeable cation concentrations, also had the highest affinity for the metals. The times required for sediment to adsorb 63% of the metals were 2.63 h, 4.08 h and 10.64 h for Pd, Pt and Rh, respectively. The FITEQL program successfully optimized the conditional binding constants of the metals on the solids from batch adsorption data. The constants decreased in the order of Pd > Rh > Pt, which was consistent with the observed high affinity of the solids for Pd. The modeling results also showed that aqueous Pd was the least sensitive to pH followed by Rh and Pt. However, metal adsorption below the points of zero net proton charges (ca. pH 6.7) is attributable to the involvement of permanent negatively charged binding sites in the adsorption process. Notably, partition coefficients, removal rates and conditional binding constants all showed a high affinity of Pd for the solids. A similarity between the model outputs and the batch adsorption data indicates the suitability of the model for describing the mobility and retention of the three metals in semi-arid soils and sediments.     

Hydrological and geochemical control of metals and arsenic in a Mediterranean river contaminated by acid mine drainage (the Amous River,France); preliminary assessment of impacts on fish (Leuciscus cephalus)

Dissolved and particulate concentrations of metals (Fe, Al, Mn, Co, Ni, Cu, Zn, Cd, Tl, Pb) and As were monitored over a 5 year period in the Amous River downstream of its confluence with a creek severely affected by acid mine drainage (AMD) originating from a former Pb–Zn mine. Water pH ranged from 6.5 to 8.8. Metals were predominantly in dissolved form, except Fe and Pb, which were in particulate form. In the particulate phase, metals were generally associated with Al oxides, whereas As was linked to Fe oxides. Metal concentrations in the dissolved and/or particulate phase were generally higher during the wet season due to higher generation of AMD. Average dissolved (size < 0.22 μm) metal concentrations (μg/L) were 1 ± 4 (Fe), 69 ± 49 (Al), 140 ± 118 (Mn), 4 ± 3 Co, 6 ± 4 (Ni), 1.3 ± 0.8 (Cu), 126 ± 81 (Zn), 1.1 ± 0.7 (Cd), 0.9 ± 0.5 (Tl), 2 ± 3 (Pb). Dissolved As concentrations ranged from 5 to 134 μg/L (30 ± 23 μg/L). During the survey, the concentration of colloidal metals (5 kDa < size < 0.22 μm) was less than 25% of dissolved concentrations. Dissolved metal concentrations were generally higher than the maximum concentrations allowed in European surface waters for priority substances (Ni, Cd and Pb) and higher than the environmental quality standards for other compounds. Using Diffusion Gradient in Thin Film (DGT) probes, metals were shown to be in potentially bioavailable form. The concentrations in Leuciscus cephalus were below the maximum Pb and Cd concentrations allowed in fish muscle for human consumption by the European Water Directive. Amongst the elements studied, only As, Pb and Tl were shown to bioaccumulate in liver tissue (As, Pb) or otoliths (Tl). Bioaccumulation of metals or As was not detected in muscle.     

Base metals and other minor elements in the manganese deposits of west-central Arkansas

Manganese oxides from deposits in west-central Arkansas were analyzed by X-ray diffraction for mineralogy and by atomic absorption spectroscopy for Mn, Fe, Co, Cu, Ni, Zn, V, Al, Li, Na, K, Mg, Ca, Sr and Ba. We report on 42 samples from 25 sites with more than 25 wt.% Mn and less than 7 wt.% Fe. Most samples were mixtures of two or more of the following minerals, many with concentric deposition: cryptomelane, lithiophorite, psilomelane and pyrolusite. In the purer samples of single minerals, lithiophorite contained the higher concentrations of total base metals (Co + Cu + Ni + Zn) than other minerals. In atom % of Mn these concentrations were: 9.51% in lithiophorite; 0.432% in psilomelane; and 0.275% in cryptomelane. The relative concentration of base metals in the pure minerals, proceeding from highest to lowest concentration, were: lithiophorite (Co = Cu > Ni > Zn); psilomelane (Co > Cu > Zn > Ni) and cryptomelane (Zn > Co = Cu > Ni).The concentration of Li correlates with the metals Al, Co, Cu, Ni and Zn, in the mineral samples containing measurable Li. Correlation coefficients (?) for Li with the various metals and sum of the base metals were: Al (? = 0.976); Co (? = 0.44); Ni (? = 0.954); Cu (? = 0.918); Zn (? = 0.875); and (Co + Cu + Ni + Zn) (? = 0.979). Li is believed to be a measure of lithiophorite. Correlation was found between Al content and base metal contents for all samples: Co (? = 0.354); Ni (? = 0.749); Cu (? = 0.808); Zn (? = 0.632); and (Co + Cu + Ni + Zn) (? = 0.884). The Al correlation extended to published values for these and the minerals hollandite and todorokite, except for Zn. Zn correlated with K in published analyses and in the eastern half of the study area where cryptomelane predominated.A mechanism is proposed to explain the enhancement by Al of base metal incorporation into manganese oxide minerals. The mechanism involves the isomorphous substitution of Al³⁺ for Mn⁴⁺ with charge neutralization by bivalent base metal ions.     

Laboratory measurements and modeling of metal-humic interactions under estuarine conditions

Equilibrium dialysis was used to measure Co- and Cu-binding by an isolated peat humic acid (PHA) in controlled laboratory experiments under simulated estuarine conditions: ionic strengths of 0.005 to 0.7 M in NaCl and mixed Na-Mg-Ca chloride solutions, with trace metal concentrations of ∼5 × 10⁻⁷ M, a PHA concentration of 10 mg/L, and at constant pH values of ∼7.8 (Co and Cu) and ∼4.6 (Cu only). Generally, Co- and Cu-humic binding decreased substantially with increasing ionic strength and, in the case of Cu, with decreasing pH. The presence of seawater concentrations of Ca and Mg had a relatively small effect on Co-humic binding and no measurable effect on that of Cu under the experimental conditions. The binding data were well-described by an equilibrium speciation code (the Windermere Humic Aqueous Model, WHAM) after optimising the fits by varying the metal-proton exchange constants for humic acid within justifiable limits (i.e., within 1 standard deviation of the mean exchange constants used in the WHAM database). The main factor producing the observed variations in metal-humic binding at constant pH was the electrostatic effect on the humic molecule. WHAM was used to predict Co- and Cu-humic binding in simulations of real estuaries. Co-humic binding is predicted to be relatively unimportant (generally <5% of total Co), whereas the Cu-humic complex is likely to be the dominant species throughout an estuary. The main factors producing changes in Co- and Cu-humic binding in the real-estuary simulations are the electrostatic effect on the humic molecule, ligand competition (mainly from carbonate species) for metals, and to a lesser extent Ca and Mg competition for humic binding sites. Variations in pH are significant only at the freshwater end of an estuary. WHAM simulations also indicated that competition effects between metals are more likely to occur in freshwaters than in seawater, due to enhanced electrostatic binding at low ionic strength.     

The nature of Cu bonding to natural organic matter

Copper biogeochemistry is largely controlled by its bonding to natural organic matter (NOM) for reasons not well understood. Using XANES and EXAFS spectroscopy, along with supporting thermodynamic equilibrium calculations and structural and steric considerations, we show evidence at pH 4.5 and 5.5 for a five-membered Cu(malate)₂-like ring chelate at 100-300 ppm Cu concentration, and a six-membered Cu(malonate))_1-2-like ring chelate at higher concentration. A “structure fingerprint” is defined for the 5.0-7.0 Å⁻¹ EXAFS region which is indicative of the ring size and number (i.e., mono- vs. bis-chelate), and the distance and bonding of axial oxygens (O_ax) perpendicular to the chelate plane formed by the four equatorial oxygens (O_eq) at 1.94 Å. The stronger malate-type chelate is a C₄ dicarboxylate, and the weaker malonate-type chelate a C₃ dicarboxylate. The malate-type chelate owes its superior binding strength to an -OH for -H substitution on the α carbon, thus offering additional binding possibilities. The two new model structures are consistent with the majority of carboxyl groups being clustered and α-OH substitutions common in NOM, as shown by recent infrared and NMR studies. The high affinity of NOM for Cu(II) is explained by the abundance and geometrical fit of the two types of structures to the size of the equatorial plane of Cu(II). The weaker binding abilities of functionalized aromatic rings also is explained, as malate-type and malonate-type structures are present only on aliphatic chains. For example, salicylate is a monocarboxylate which forms an unfavorable six-membered chelate, because the OH substitution is in the β position. Similarly, phthalate is a dicarboxylate forming a highly strained seven-membered chelate.Five-membered Cu(II) chelates can be anchored by a thiol α-SH substituent instead of an alcohol α-OH, as in thio-carboxylic acids. This type of chelate is seldom present in NOM, but forms rapidly when Cu(II) is photoreduced to Cu(I) at room temperature under the X-ray beam. When the sample is wet, exposure to the beam can reduce Cu(II) to Cu(0). Chelates with an α-amino substituent were not detected, suggesting that malate-like α-OH dicarboxylates are stronger ligands than amino acids at acidic pH, in agreement with the strong electronegativity of the COOH clusters. However, aminocarboxylate Cu(II) chelates may form after saturation of the strongest sites or at circumneutral pH, and could be observed in NOM fractions enriched in proteinaceous material. Overall, our results support the following propositions:

(1)

The most stable Cu-NOM chelates at acidic pH are formed with closely-spaced carboxyl groups and hydroxyl donors in the α-position; oxalate-type ring chelates are not observed.

(2)

Cu(II) bonds the four equatorial oxygens to the heuristic distance of 1.94 ± 0.01 Å, compared to 1.97 Å in water. This shortening increases the ligand field strength, and hence the covalency of the Cu-O_eq bond and stability of the chelate.

(3)

The chelate is further stabilized by the bonding of axial oxygens with intra- or inter-molecular carboxyl groups.

(4)

Steric hindrances in NOM are the main reason for the absence of Cu-Cu interactions, which otherwise are common in carboxylate coordination complexes.

     

Iron,manganese and trace metal concentrations in seaweeds from the central west coast of the Gulf of California

Concentrations of Co, Cu, Fe, Mn, Ni, Pb and Zn in four macroalgae species (Ulva lactuca, Chondracanthus squarrulosus, Sargassum sinicola and Gracilariopsis lemaneiformis) were obtained for the first time from the central part of the west coast of the Gulf of California. Generally, no differences in metal concentrations were found among the different seaweed species, although spatial differences were apparent. Iron, Mn and Cu exhibited higher concentrations at the stations located in front of Angel de la Guarda Island, probably because of high vertical mixing processes present in the zone. The results were compared with dissolved metal concentrations reported for the Gulf of California (Cd, Mn and Fe) and the North Pacific Ocean. The resulting linear regression of the results vs. North Pacific Ocean concentrations indicated that the levels of Cu, Ni and Zn measured in this study were within its 95% confidence level. Furthermore, this comparison was capable of detecting dissolved Fe and Mn enrichments in Gulf of California waters relative to the North Pacific Ocean concentrations. Calculations of total masses of metals associated with algal biomass on the west coast of the Gulf of California indicated that the lowest masses were represented by Cu (108 ± 25 kg) and Ni (184 ± 52 kg), whereas Pb (1.1 ± 0.6 ton) and Fe (10.9 ± 8.5 ton) were the elements with the highest associated masses.     

The cycling of Ni,Zn, Cu in the system “mine tailings–ground water–plants”: A case study

The comparative behaviour of Ni, Cu and Zn in the system “mine tailings–ground water–plants” has been investigated at the Ni–Cu mine site operated by INCO Ltd. Thompson Operations, Thompson, Manitoba. Oxidation of sulphide minerals causes the release of metals from exposed tailings containing Ni ∼2000 ppm, Cu ∼150 ppm and Zn ∼100 ppm to the ground water, which contains 350 mg/L Ni, 0.007 mg/L Cu, and 1.6 mg/L Zn. The metal concentration in the ground water is affected by the relative proportions of sulfide minerals, the rate of oxidation of sulphide minerals (Ni-bearing pyrrhotite > sphalerite > chalcopyrite), and the affinity of the metals for secondary Fe-phases (Ni > Zn > Cu).     

Nanoparticles in natural systems I: The effective reactive surface area of the natural oxide fraction in field samples

Information on the particle size and reactive surface area of natural samples is essential for the application of surface complexation models (SCM) to predict bioavailability, toxicity, and transport of elements in the natural environment. In addition, this information will be of great help to enlighten views on the formation, stability, and structure of nanoparticle associations of natural organic matter (NOM) and natural oxide particles.Phosphate is proposed as a natively present probe ion to derive the effective reactive surface area of natural samples. In the suggested method, natural samples are equilibrated (?10 days) with 0.5 M NaHCO₃ (pH = 8.5) at various solid-solution ratios. This matrix fixes the pH and ionic strength, suppresses the influence of Ca²⁺ and Mg²⁺ ions by precipitation these in solid carbonates, and removes NOM due to the addition of activated carbon in excess, collectively leading to the dominance of the PO₄-CO₃ interaction in the system. The data have been interpreted with the charge distribution (CD) model, calibrated for goethite, and the analysis results in an effective reactive surface area (SA) and a reversibly bound phosphate loading Γ for a series of top soils.The oxidic SA varies between about 3-30 m²/g sample for a large series of representative agricultural top soils. Scaling of our data to the total iron and aluminum oxide content (dithionite-citrate-bicarbonate extractable), results in the specific surface area between about 200-1200 m²/g oxide for most soils, i.e. the oxide particles are nano-sized with an equivalent diameter in the order of ∼1-10 nm if considered as non-porous spheres. For the top soils, the effective surface area and the soil organic carbon fraction are strongly correlated. The oxide particles are embedded in a matrix of organic carbon (OC), equivalent to ∼1.4 ± 0.2 mg OC/m² oxide for many soils of the collection, forming a NOM-mineral nanoparticle association with an average NOM volume fraction of ∼80%. The average mass density of such a NOM-mineral association is ∼1700 ± 100 kg/m³ (i.e. high-density NOM). The amount of reversibly bound phosphate is rather close to the amount of phosphate that is extractable with oxalate. The phosphate loading varies remarkably (Γ ≈ 1-3 μmol/m² oxide) in the samples. As discussed in part II of this paper series (Hiemstra et al., 2010), the phosphate loading (Γ) of field samples is suppressed by surface complexation of NOM, where hydrophilic, fulvic, and humic acids act as a competitor for (an)ions via site competition and electrostatic interaction.     

Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO₃ electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (⁶⁵Cu/⁶³Cu) and Zn (⁶⁶Zn/⁶⁴Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (α_soln-solid) are 0.99927 ± 0.00008 for Cu and 0.99948 ± 0.00004 for Zn or, alternately, the separation factors (Δ_soln-solid) are −0.73 ± 0.08‰ for Cu and −0.52 ± 0.04‰ for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).     

Structural environments of carboxyl groups in natural organic molecules from terrestrial systems. Part 1: Infrared spectroscopy

Carboxyls play an important role in the chemistry of natural organic molecules (NOM) in the environment, and their behavior is dependent on local structural environment within the macromolecule. We studied the structural environments of carboxyl groups in dissolved NOM from the Pine Barrens (New Jersey, USA), and IHSS NOM isolates from soils and river waters using attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy. It is well established that the energies of the asymmetric stretching vibrations of the carboxylate anion (COO⁻) are sensitive to the structural environment of the carboxyl group. These energies were compiled from previous infrared studies on small organic acids for a wide variety of carboxyl structural environments and compared with the carboxyl spectral features of the NOM samples. We found that the asymmetric stretching peaks for all NOM samples occur within a narrow range centered at 1578 cm⁻¹, suggesting that all NOM samples examined primarily contain very similar carboxyl structures, independent of sample source and isolation techniques employed. The small aliphatic acids containing hydroxyl (e.g., d-lactate, gluconate), ether/ester (methoxyacetate, acetoxyacetate), and carboxylate (malonate) substitutions on the α-carbon, and the aromatic acids salicylate (ortho-OH) and furancarboxylate (O-heterocycle), exhibit strong overlap with the NOM range, indicating that similar structures may be common in NOM. The width of the asymmetric peak suggests that the structural heterogeneity among the predominant carboxyl configurations in NOM is small. Changes in peak area with pH at energies distant from the peak at 1578 cm⁻¹, however, may be indicative of a small fraction of other aromatic carboxyls and aliphatic structures lacking α-substitution. This information is important in understanding NOM-metal and mineral-surface complexation, and in building appropriate structural and mechanistic models of humic materials.     

Seasonal dripwater Mg/Ca and Sr/Ca variations driven by cave ventilation: Implications for and modeling of speleothem paleoclimate records

A 4-year study in a central Texas cave quantifies multiple mechanisms that control dripwater composition and how these mechanisms vary at different drip sites. We monitored cave-air compositions, in situ calcite growth, dripwater composition and drip rate every 4-6 weeks. Three groups of drip sites are delineated (Groups 1-3) based on geochemical variations in dripwater composition. Quantitative modeling of mineral-solution reactions within the host carbonate rock and cave environments is used to identify mechanisms that can account for variations in dripwater compositions. The covariation of Mg/Ca (and Sr/Ca) and Sr isotopes is key in delineating whether Mg/Ca and Sr/Ca variations are dictated by water-rock interaction (i.e., calcite or dolomite recrystallization) or prior calcite precipitation (PCP). Group 1 dripwater compositions reflects a narrow range of the extent of water-rock interaction followed by varying amounts of prior calcite precipitation (PCP). Group 2 dripwater compositions are controlled by varying amounts of water-rock interaction with little to no PCP influence. Group 3 dripwater compositions are dictated by variable extents of both water-rock interaction and PCP. Group 1 drip sites show seasonal variations in dripwater Mg/Ca and Sr/Ca, whereas the other drip sites do not. In contrast to the findings of most previous dripwater Mg/Ca-Sr/Ca studies, these seasonal variations (at Group 1 drip sites) are independent of changes in water flux (i.e., rainfall and/or drip rate), and instead significantly correlate with changes in cave-air CO₂ concentrations. These results are consistent with lower cave-air CO₂, related to cool season ventilation of the cave atmosphere, enhancing calcite precipitation and leading to dripwater geochemical evolution via PCP. Group 1 dripwater Mg/Ca and Sr/Ca seasonality and evidence for PCP as a mechanism that can account for that seasonality, have two implications for many other regions where seasonal ventilation of caves is likely: (1) speleothem trace-element records may provide seasonal signals, and (2) such records may be biased toward recording climate conditions during the season when calcite is depositing. Additionally, we use our results to construct a forward model that illustrates the types of speleothem Mg/Ca and Sr/Ca variations that would result from varying controls on dripwater compositions. The model provides a basis for interpreting paleo-dripwater controls from high frequency Mg/Ca and Sr/Ca variations for speleothems from caves at which long term monitoring studies are not feasible.     

Contamination assessment and health risk of heavy metals in dust from Changqing industrial park of Baoji,NW China

The contents of Co, Cr, Cu, Mn, Ni, Pb and Zn in the dust samples collected from Changqing industrial park of Baoji city, NW China, were measured by XRF, while As and Hg in the dust samples were analyzed by AFS. Geo-accumulation index (I _geo), pollution index (PI) and integrated pollution index (IPI) were calculated to evaluate the heavy metal contamination level of dust. The health risk due to exposure to heavy metals in dust was analyzed by the Health Risk Assessment Model of US EPA. The results show that the arithmetic means of As, Co, Cr, Cu, Hg, Mn, Ni, Pb and Zn are 23.3, 16.4, 1591.8, 178.2, 0.243, 346.5, 40.2, 1,586.2 and 1,918.8 mg kg^?1, respectively, which are higher than the background values of Shaanxi soil, especially for Cr, Cu, Hg, Pb, and Zn. The mean values of I _geo reveal the order of Pb > Zn > Cr > Hg > Cu > As > Co > Ni > Mn. The high I _geo of Cr, Cu, Hg, Pb and Zn in dust indicates that there is considerable pollution from Cr, Cu, Hg, Pb and Zn, while the low I _geo of As, Co, Mn and Ni presents no pollution in dust. The assessment results of PI support the results of I _geo, and IPI indicates heavy metals in dust polluted seriously. The health risk assessment shows that ingestion of dust particles is the route for exposure to heavy metals from dust, followed by dermal adsorption. Exposure to As, Cr and Pb from dust may pose a potential health threat to children and adults. The risk of cancer from As, Co, Cr and Ni due to dust exposure is low.     

Iron-hydroxide, iron-sulfate and hydrous-silica coatings in acid-mine tailings facilities: A comparative study of their trace-element composition

Surface alteration-layers often coat minerals in acid-mine drainage systems and the characterization of their chemical composition is required to understand the uptake or release of potentially toxic elements. Samples with micrometer-thick rock coatings were collected from bedrock in contact with three acidic tailings ponds and a small lake, all located within the Copper Cliff mine tailings disposal area in Sudbury, Ontario, Canada. Distribution and concentration of trace-metals in the rock coatings were characterized with Laser-Ablation Inductively-Coupled Plasma Mass Spectroscopy and Micro X-ray Fluorescence Spectroscopy. The rock coatings are composed of goethite, ferrihydrite, schwertmannite, jarosite and amorphous silica. The latter phase is a product of the non-stoichiometric weathering of the underlying siliceous rock. Layers within the coatings are distinguished on the basis of their atomic Fe:Si ratios: FeO_x coatings have Fe:Si > 4:1, Si-FeO_x coatings have Fe:Si = 4:1 to 1:1 and SiO_x coatings have Si > Fe. Iron-rich coatings (FeO_x) in contact with acidic tailings ponds (pH < 3.5) have lower trace-metal concentrations than their Si-rich counterparts, whereas FeO_x in contact with lake water at near neutral pH have similar trace-metal concentrations than Si-FeO_x and SiO_x, most likely the result of higher adsorption rates of metals at near neutral pH conditions. High trace-metal concentrations in Si-FeO_x and SiO_x are explained by the presence of jarosite-group minerals, which formed within Si-rich alteration layers through mixing of leached alkaline cations and trace elements from the underlying rock and Fe³⁺-sulfate solutions from the pond. Calculated enrichment factors for trace metals and metalloids in the coatings (relative to the pond) indicate that the mobility for Pb, As, Cr and Cu in the upper part of tailings ponds is commonly lower than the mobility for Zn, Mn, Co and Ni. The environmental significance of these findings is discussed in terms of the attenuation of trace metals in the coatings and the widespread occurrences of silica gels and jarosite-group minerals.     

Environmental impacts of heavy metals (Co, Cu, Pb, Zn) in surficial sediments of estuary in Daliao River and Yingkou Bay (northeast China): concentration level and chemical fraction

Heavy metal pollution in the surficial sediments derived from the estuary in Daliao River and Yingkou Bay is investigated to assess environmental quality, pollution level, bioavailability and toxicity. The ranges of Pb, Co, Zn and Cu concentrations in the surficial sediments are: 16.57–39.18, 3.61–16.02, 16.53–39.18, 2.77–43.80 mg/kg. Results of the geoaccumulation index (I _geo) show that the pollution levels of four metals are in the “unpolluted” class except for Pb in 15 sampling sites. The pollution level of the study area assessed by pollution load index (PLI) shows that except for the moderately polluted region of sites 1, 2, 3, 8, 12 and 13, other sites belong to unpolluted state. The sequence of pollution extent of different heavy metals is: Pb > Zn > Co > Cu. At all sampling sites, the grades of potential ecological risk of Co, Cu, Pb and Zn are “light”. The order of potential ecological risk is: Pb > Co > Cu > Zn. Sequential extraction of the metals indicates that the states of Pb, Cu, Co and Zn in the sediment are relatively stable at most sites of the estuary in Daliao River and Yingkou Bay, which means that there is a low source of pollution arriving in this area. While only at several sites, Co, Pb and Zn are labile, which are considered as anthropogenically originated.     

The mobility,bioavailability, and human bioaccessibility of trace metals in urban soils of Hong Kong

Trace metals in soils may pose risks to both ecosystem and human health, especially in an urban environment. However, only a fraction of the metal content in soil is mobile and/or available for biota uptake and human ingestion. Various environmental availabilities of trace metals (Cu, Pb and Zn) in topsoil from highly urbanized areas of Hong Kong to plants, organisms, and humans, as well as the leaching potential to groundwater were evaluated in the present study. Forty selected soil samples were extracted with 0.11 M acid acetic, 0.01 M calcium chloride, 0.005 M diethylenetriaminepentaacetic acid, and simplified physiologically based extraction tests (PBET) for the operationally defined mobilizable, effectively bioavailable, potentially bioavailable, and human bioaccessible metal fractions, respectively. The metals were generally in the order of Zn > Cu ∼ Pb for both mobility (24%, 7.6%, 6.7%) and effective bioavailability (2.8%, 0.9%, 0.6%), Pb (18%) > Cu (13%) > Zn (7.4%) for potential bioavailability, and Pb (59%) ∼ Cu (58%) > Zn (38%) for human bioaccessibility. Although the variations in the different available concentrations of metals could mostly be explained by total metal concentrations in soil, the regression model predictions were further improved by the incorporation of soil physicochemical properties (pH, OM, EC). The effectively bioavailable Zn and Pb were mostly related to soil pH. Anthropogenic Pb in urban soils tended to be environmentally available as indicated by Pb isotopic composition analysis. Combining various site-specific environmental availabilities might produce a more realistic estimation for the integrated ecological and human health risks of metal contamination in urban soils.