Time-dependent changes of zinc speciation in four soils contaminated with zincite or sphalerite

The long-term speciation of Zn in contaminated soils is strongly influenced by soil pH, clay, and organic matter content as well as Zn loading. In addition, the type of Zn-bearing contaminant entering the soil may influence the subsequent formation of pedogenic Zn species, but systematic studies on such effects are currently lacking. We therefore conducted a soil incubation study in which four soils, ranging from strongly acidic to calcareous, were spiked with 2000 mg/kg Zn using either ZnO (zincite) or ZnS (sphalerite) as the contamination source. The soils were incubated under aerated conditions in moist state for up to four years. The extractability and speciation of Zn were assessed after one, two, and four years using extractions with 0.01 M CaCl(2) and Zn K-edge X-ray absorption fine structure (XAFS) spectroscopy, respectively. After four years, more than 90% of the added ZnO were dissolved in all soils, with the fastest dissolution occurring in the acidic soils. Contamination with ZnO favored the formation of Zn-bearing layered double hydroxides (LDH), even in acidic soils, and to a lesser degree Zn-phyllosilicates and adsorbed Zn species. This was explained by locally elevated pH and high Zn concentrations around dissolving ZnO particles. Except for the calcareous soil, ZnS dissolved more slowly than ZnO, reaching only 26 to 75% of the added ZnS after four years. ZnS dissolved more slowly in the two acidic soils than in the near-neutral and the calcareous soil. Also, the resulting Zn speciation was markedly different between these two pairs of soils: Whereas Zn bound to hydroxy-interlayered clay minerals (HIM) and octahedrally coordinated Zn sorption complexes prevailed in the two acidic soils, Zn speciation in the neutral and the calcareous soil was dominated by Zn-LDH and tetrahedrally coordinated inner-sphere Zn complexes. Our results show that the type of Zn-bearing contaminant phase can have a significant influence on the formation of pedogenic Zn species in soils. Important factors include the rate of Zn release from the contaminant phases and effects of the contaminant phase on bulk soil properties and on local chemical conditions around weathering contaminant particles.     

Changes in uranium speciation through a depth sequence of contaminated Hanford sediments

The disposal of basic sodium aluminate and acidic U(VI)-Cu(ll) wastes in the now-dry North and South 300 A Process Ponds atthe Hanford site resulted in a groundwater plume of U(VI). To gain insight into the geochemical processes that occurred during waste disposal and those affecting the current and future fate and transport of this uranium plume, the solid-phase speciation of uranium in a depth sequence of sediments from the base of the North Process Pond through the vadose zone to groundwater was investigated using standard chemical and mineralogical analyses, electron and X-ray microprobe measurements, and X-ray absorption fine structure spectroscopy. Near-surface sediments contained uranium coprecipitated with calcite, which formed due to overneutralization of the waste ponds with base (NaOH). At intermediate depths in the vadose zone, metatorbernite [Cu(UO2PO4)2 x 8H2O] precipitated, likely during pond operations. Uranium occurred predominantly sorbed onto phyllosilicates in the deeper vadose zone and groundwater; sorbed uranium was also an important component at intermediate depths. Since the calcite-bearing pond sediments have been removed in remediation efforts, uranium fate and transport will be controlled primarily by desorption of the sorbed uranium and dissolution of metatorbernite.     

Changes in zinc speciation in field soil after contamination with zinc oxide

Recent studies on the speciation of Zn in contaminated soils confirmed the formation of Zn-layered double hydroxide (LDH) and Zn-phyllosilicate phases. However, no information on the kinetics of the formation of those phases under field conditions is currently available. In the present study, the transformation of Zn in a field soil artificially contaminated with ZnO containing filter dust from a brass foundry was monitored during 4 years using extended X-ray absorption fine structure (EXAFS) spectroscopy. Soil sections were studied by micro-X-ray fluorescence (micro-XRF) and micro-EXAFS spectroscopy. EXAFS spectra were analyzed by principal component analysis (PCA) and linear combination fitting (LCF). The results show that ZnO dissolved within 9 months and that half of the total Zn reprecipitated. The precipitate was mainly of the Zn-LDH type (>75%). Only a minor fraction (<25%) may be of Zn-phyllosilicate type. The remaining Zn was adsorbed to soil organic and inorganic particles. No significant changes in Zn speciation occurred from 9 to 47 months after the contamination. Thermodynamic calculations show that both Zn-LDH and Zn-phyllosilicate may form in the presence of ZnO but that the formation of Zn-phyllosilicate would be thermodynamically favored. Thus, the dominance of Zn-LDH found by spectroscopy suggests that the formation of the Zn precipitates was not solely controlled bythermodynamics but also contained a kinetic component. The rate-limiting step could be the supply of Al and Si from soil minerals to the Zn-rich solutions around dissolving ZnO grains.     

Changes in zinc speciation with mine tailings acidification in a semiarid weathering environment

High concentrations of residual metal contaminants in mine tailings can be transported easily by wind and water, particularly when tailings remain unvegetated for decades following mining cessation, as is the case in semiarid landscapes. Understanding the speciation and mobility of contaminant metal(loid)s, particularly in surficial tailings, is essential to controlling their phytotoxicities and to revegetating impacted sites. In prior work, we showed that surficial tailings samples from the Klondyke State Superfund Site (AZ, USA), ranging in pH from 5.4 to 2.6, represent a weathering series, with acidification resulting from sulfide mineral oxidation, long-term Fe hydrolysis, and a concurrent decrease in total (6000 to 450 mg kg(-1)) and plant-available (590 to 75 mg kg(-1)) Zn due to leaching losses and changes in Zn speciation. Here, we used bulk and microfocused Zn K-edge X-ray absorption spectroscopy (XAS) data and a six-step sequential extraction procedure to determine tailings solid phase Zn speciation. Bulk sample spectra were fit by linear combination using three references: Zn-rich phyllosilicate (Zn(0.8)talc), Zn sorbed to ferrihydrite (Zn(adsFeOx)), and zinc sulfate (ZnSO(4) · 7H(2)O). Analyses indicate that Zn sorbed in tetrahedral coordination to poorly crystalline Fe and Mn (oxyhydr)oxides decreases with acidification in the weathering sequence, whereas octahedral zinc in sulfate minerals and crystalline Fe oxides undergoes a relative accumulation. Microscale analyses identified hetaerolite (ZnMn(2)O(4)), hemimorphite (Zn(4)Si(2)O(7)(OH)(2) · H(2)O) and sphalerite (ZnS) as minor phases. Bulk and microfocused spectroscopy complement the chemical extraction results and highlight the importance of using a multimethod approach to interrogate complex tailings systems.     

Arsenic speciation and phytoavailability in contaminated soils using a sequential extraction procedure and XANES spectroscopy

In this study, a sequential extraction procedure (SEP) and X-ray absorption near edge structure (XANES) spectroscopy were used to determine the solid-phase speciation and phytoavailability of arsenic (As) of historically contaminated soils from As containing pesticides and herbicides and soils spiked with As in the laboratory. Brassica juncea was grown in the contaminated soils to measure plant available As in a glasshouse experiment. Arsenic associated with amorphous Fe oxides was found to be the dominant phase using both SEP and XANES spectroscopy. Arsenic predominantly existed in arsenate (As(V)) form in the soils; in a few samples As was also present in arsenite (As(III)) form or in scorodite mineral. Arsenic concentration in shoots showed significant (p < 0.001-0.05) correlations with the exchangeable As (r = 0.85), and amorphous Fe oxides associated As evaluated by the SEP (r = 0.67), and As associated with amorphous Fe oxides as determined by XANES spectroscopy (r = 0.51). The results show that As in both fractions was readily available for plant uptake and may pose a potential risk to the environment. The combination of SEP and XANES spectroscopy allowed us the quantitative speciation of As in the contaminated soils and the identification of valence and mineral forms of As. Such detailed knowledge on As speciation and availability is vital for management and rehabilitation of As-contaminated soils.     

Arsenic speciation in blue mussels (Mytilus edulis) along a highly contaminated arsenic gradient

Arsenic is naturally present in marine ecosystems, and these can become contaminated from mining activities, which may be of toxicological concern to organisms that bioaccumulate the metalloid into their tissues. The toxic properties of arsenic are dependent on the chemical form in which it is found (e.g., toxic inorganic arsenicals vs nontoxic arsenobetaine), and two analytical techniques, high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) and X-ray absorption spectroscopy (XAS), were used in the present study to examine the arsenic species distribution in blue mussels (Mytilus edulis) obtained from an area where there is a strong arsenic concentration gradient as a consequence of mining impacted sediments. A strong positive correlation was observed between the concentration of inorganic arsenic species (arsenic compounds with no As-C bonds) and total arsenic concentrations present in M. edulis tissues (R(2) = 0.983), which could result in significant toxicological consequences to the mussels and higher trophic consumers. However, concentrations of organoarsenicals, dominated by arsenobetaine, remained relatively constant regardless of the increasing As concentration in M. edulis tissue (R(2) = 0.307). XANES bulk analysis and XAS two-dimensional mapping of wet M. edulis tissue revealed the presence of predominantly arsenic-sulfur compounds. The XAS mapping revealed that the As(III)-S and/or As(III) compounds were concentrated in the digestive gland. However, arsenobetaine was found in small and similar concentrations in the digestive gland as well as the surrounding tissue suggesting arsenobetaine may being used in all of the mussel's cells in a physiological function such as an intracellular osmolyte.     

Solid-solution speciation and phytoavailability of copper and zinc in soils

The soil solution speciation and solid-phase fractionation of copper (Cu) and zinc (Zn) in 11 typical uncontaminated soils of South Australia were assessed in relation to heavy metal phytoavailability. The soils were analyzed for pH (4.9-8.4), soil organic matter content (3.5 to 23.8 g of C kg(-1)), total soil solution metal concentrations, Cu8 (49-358 microg kg(-1)) and Zn8 (121-582 microg kg(-1)), and dissolved organic matter (DOM) (69-827 mg of C L(-1)). The solid-liquid partition coefficient (Kd) ranged from between 13.9 and 152.4 L kg(-1) for Cu and 22.6 to 266.3 L kg(-1) for Zn. The phytoavailability of Cu and Zn could be predicted significantly using an empirical model with the solid-phase fractions of Cu and Zn, as obtained from selective sequential extraction scheme, as components. Phytoavailable Cu and Zn were found to significantly correlate with fulvic complex Cu (r= 0.944, P < 0.0001) and exchangeable Zn (r = 0.832, P = 0.002), respectively. The fulvic complex Cu was found to explain 89.2% of the variation in phytoavailable Cu, where as, the exchangeable Zn together with fulvic complex Zn could explain 78.9% of the variation in phytoavailable Zn. The data presented demonstrate the role of solid-phase metal fractions in understanding the heavy metal phytoavailability. The assessment of the role of solid-phase fractions in heavy metal phytoavailability is a neglected area of study and deserves close attention.     

Seasonal temperature fluctuations induces rapid inactivation of Cryptosporidium parvum

This study measured the inactivation rate of bovine genotype A Cryptosporidium parvum oocysts attributable to diurnal oscillations of ambient temperature and solar radiation typical of California rangelands and dairies from spring through autumn. We first measured the relationship between air temperature and the internal temperature of bovine feces exposed to sunlight on commercial operations throughout California. Once maximum air temperature exceeded the mid 20 degrees C, diurnal thermal regimes of bovine fecal material exhibited peaks of over 40, 50, 60, and 70 degrees C. These diurnal thermal regimes were emulated using a thermocycler, with oocysts suspended in distilled water or fecal-water mix. Using oral inoculations of 10(5) C. parvum oocysts per neonatal Balb/c mouse (>1000-fold the ID50), no infections were observed using 1 to 5-day cycles of these thermal regimes. Loss of infectivity induced bythese thermal regimes was primarily due to partial or complete in vitro excystation during the first 24-h diurnal cycle and secondarily to thermal inactivation of the remaining intact or partial oocysts. These results suggest that as ambient conditions generate internal fecal temperatures > or = 40 degrees C via conduction, radiation, and convection, rapid environmental inactivation occurs at a rate of > or = 3.27 log reduction d(-1) for C. parvum oocysts deposited in the feces of cattle.     

Speciation and release kinetics of zinc in contaminated paddy soils

Zinc is an important nutrient for plants, but it can be toxic at high concentrations. The solubility and speciation of Zn is controlled by many factors, especially soil pH and Eh, which can vary in lowland rice culture. This study determined Zn speciation and release kinetics in Cd-Zn cocontaminated alkaline and acidified paddy soils, under various flooding periods and draining conditions, by employing synchrotron-based techniques and a stirred-flow kinetic method. Results showed almost no change in Zn speciation and release kinetics in the two soils, although the soils were subjected to different flooding periods and draining conditions. The mineral phases in which Zn is immobilized in the soil samples were constrained by linear least squares fitting (LLSF) analyses of bulk X-ray absorption fine structure (XAFS) spectra. Only two main phases were identified by LLSF, i.e., Zn-layered double hydroxides (Zn/Mg-hydrotalcite-like, and ZnAl-LDH) and Zn-phyllosilicates (Zn-kerolite). Under all soil pHs, flooding, and draining conditions, less than 22% of Zn was desorbed from the soil after a two-hour desorption experiment. The information on Zn chemistry obtained in this study will be useful in finding the best strategy to control Cd and Zn bioavailability in the Cd-Zn cocontaminated paddy soils.     

Seasonal varability of metals transport through a wetland impacted by mine drainage in the Rocky Mountains

An annual study of a natural wetland receiving drainage with high concentrations of iron, zinc, and manganese from an abandoned mine tunnel was conducted. During summer, the wetland reduced the mass flow from the tunnel to a receiving stream by more than 90% for iron, by 65% for zinc, and by 25% for manganese. Plant uptake accounted for less than 1% of the total retention. Zinc and manganese mass flows to the stream were greater than mass flows from the tunnel during autumn and winter, indicating a seasonal cycle of the wetland acting as a net sink in the summer and then a net source in the winter. Iron mass flow to the stream was less than the iron mass flow from the tunnel for the majority of the year, with the high retention of iron in the wetland associated with large deposits of iron oxides, especially thick in the upper reaches of the wetland. Spring snowmelt saturated the otherwise dry material in the mine tailings above the wetland, creating an additional source of inflow, with metal concentrations two times higher and three pH units lower than water flowing from the mine tunnel. This period of runoff from the tailings, with the associated high concentration of metals in the stream below the wetland, represented a critical time for stream biota.     

Spatial and temporal variability of arsenic solid-state speciation in historically lead arsenate contaminated soils

The arsenic (As) solid-state speciation (i.e., oxidation state, precipitates, and adsorption complexes) is one of the most important factors controlling dissolved As concentrations at As contaminated sites. In this case study, two representative subsurface samples (i.e., oxidized and semi-reduced sites) from former lead arsenate contaminated soils in the northeastern United States were chosen to investigate the effects of aging on As retention mechanisms using multiscale spectroscopic techniques. X-ray powder diffraction (XRD), synchrotron based microfocused (micro) XRD, in situ micro-synchrotron based X-ray fluorescence spectroscopy (SXRF), and micro-X-ray absorption near edge structure (XANES) spectroscopy were used to compliment the final bulk X-ray absorption spectroscopy (XAS) analyses. In the sample from an oxic area, As is predominantly (approximately 71%) present as As(V) adsorbed onto amorphous iron oxyhydroxides with a residue (approximately 29%) of an original contaminant, schultenite (PbHAsO4). Contrarily, there is no trace of schultenite in the sample from a semi-reduced area. Approximately 25% of the total As is present as adsorbed phases on amorphous iron oxyhydroxide and amorphous orpiment (As2S3). The rest of the fractions (approximately 46%) were identified as As(V)-Ca coprecipitates. This study shows that aging effects can significantly alter the original chemical constituent (schultenite) in soils, resulting in multi and site-specific As solid-state speciation. The variability in spatial and temporal scale may be important in assessing the environmental risk and in developing in situ remediation technologies.     

Influence of metal speciation in natural freshwater on bioaccumulation of copper and zinc in periphyton: a microcosm study

The free ion activity model (FIAM) has already been confirmed under laboratory conditions for many trace metals but has still to be validated under natural conditions where the presence of natural organic ligands influences metal speciation and bioavailability. The goal of this study was to test if the FIAM is followed under natural conditions by measuring copper and zinc speciation as well as metal accumulation in periphyton. Periphyton was exposed in microcosms to natural river water with different added concentrations of copper (25-258 nM) or zinc (18-501 nM) and additions of a synthetic ligand (NTA). Free Cu2+ was in the range of 10(-16.5)-10(-14.5) M and Zn(2+) was in the range of 0.7-8.7 nM, as measured by competitive ligand exchange coupled with cathodic/anodic stripping voltammetry. Other metal complexes were either measured or computed. Bioaccumulation of zinc in periphyton appeared to be controlled by the free zinc ion concentration, confirming the FIAM. In contrast, bioaccumulation of copper was controlled by weakly complexed copper (including Cu2+ plus inorganic and weak organic complexes), which is in disagreement with the FIAM, and appears to be caused by limitation of copper diffusion due to very low free Cu2+ occurring in natural environments.     

PCB and PAH speciation among particle types in contaminated harbor sediments and effects on PAH bioavailability

This research provides particle-scale understanding of PCB and PAH distribution in sediments obtained from three urban locations in the United States: Hunters Point, CA; Milwaukee Harbor, WI; and Harbor Point, NY. The sediments comprised mineral grains (primarily sand, silt, and clays) and carbonaceous particles (primarily coal, coke, charcoal, pitch, cenospheres, and wood). The carbonaceous sediment fractions were separated from the mineral fractions based on their lower density and were identified by petrographic analysis. In all three sediments, carbonaceous particles contributed 5-7% of the total mass and 60-90% of the PCBs and PAHs. The production of carbonaceous particles is not known to be associated with PCB contamination, and it is very unlikely that these particles can be the source of PCBs in the environment Thus, it appears that carbonaceous particles preferentially accumulate PCBs acting as sorbents in the aqueous environment if PCBs are released directly to the sediment or if deposited as airborne soot particles. Aerobic bioslurry treatment resulted in negligible PAH loss from the carbonaceous coal-derived material in Milwaukee Harbor sediment but resulted in 80% of the PAHs being removed from carbonaceous particles in Harbor Point sediment. Microscale PAH extraction and analysis revealed that PAHs in Harbor Point sediment were associated mainly with coal tar pitch residue. PAHs present in semisolid coal tar pitch are more bioavailable than PAHs sorbed on carbonaceous particles such as coal, coke, charcoal, and cenosphere. Results of this study illustrate the importance of understanding particle-scale association of hydrophobic organic contaminants for explaining bioavailability differences among sediments.     

Physical and kinetic speciation of copper and zinc in three geochemically contrasting marine estuaries

The physical and kinetic speciation of Cu and Zn in three impacted marine estuaries was examined. Contrasts in sources of metal-binding ligands, solution chemistry, and hydrologic forcing between and withinthethree study systems (Cape Fear River Estuary, North Carolina; Norfolk-Hampton Roads-Elizabeth River, Virginia; San Diego Bay, California) were exploited to enhance our understanding of Cu and Zn speciation. Trace metal-optimized tangential-flow ultrafiltration at 1 kDa nominal molecular weight limit (NMWL) was used to fractionate <0.4 microm species into colloidal and "dissolved" pools. Colloidal species of dissolved organic matter (DOM) and copper were significant and often the dominant pools in each of the three study systems. Characteristic colloidal fractions of both DOM and Cu ranged from near 70% of <0.4 microm concentrations in Cape Fear to 50% in San Diego Bay. Colloidal Cu and DOM were strongly coupled, and variability in observed <0.4 microm Cu concentrations was closely related to the concentrations of colloidal-associated metal. Colloidal fractions were much smaller for Zn than that of Cu; ranging from 10-30% in Cape Fear to less than 5% in San Diego Bay, and no relationship to DOM was observed. Kinetic separations on Chelex resin revealed the presence of large nonlabile pools of Cu in each of the study systems, with the highest fractions (70-100%) in Cape Fear and Norfolk and lowest (30-50%) in San Diego Bay. A close relationship was observed between colloidal and nonlabile Cu species, implying slow reactivity of colloidal-bound Cu. The fraction of filterable Zn labile to Chelex averaged 97%, 85%, and 60% in San Diego, Norfolk, and Cape Fear, respectively. Anthropogenic Zn appeared almost exclusively in the <1 kDa fraction, while anthropogenic Cu was distributed between dissolved and colloidal pools. Copper particle-partition coefficients (Kd) followed the trend: San Diego > Norfolk > Cape Fear and were inversely correlated with DOC concentrations. Colloid-based partition coefficients were significantly greater, in many cases an order of magnitude greater, than particle-based partition coefficients. The partitioning data suggest the presence of metal-enriched bacterial-derived exudates and/or discrete metal phases in colloidal-sized particles in impacted regions of these estuaries. The strong relationships observed between Cu and DOC indicate that Cu partitioning behavior over a range of estuarine environments may be modeled effectively with a limited set of coefficients. Our measurements of metal lability and size distribution imply that the fraction of <0.4 microm Zn that is likely to be bioavailable is greater than that for Cu, especially in impacted regions of the study systems.     

Uptake of copper,nickel and zinc by crops growing in contaminated soils

A series of three replicated pot trials is reported in which various crops were grown in soils having enhanced concentrations of copper, nickel and zinc. Concentrations of these elements in the tops of plants harvested at their most sensitive stage were compared with ‘total’ and ‘extractable’ concentrations in soil and with concentrations in soil solutions. There was little difference between the relationships of ‘total’ and ‘extractable’ soil metal and concentrations in plant tissue. In general, the correlation between concentrations of metals in soils and plants was unpredictable. Plants differed in their efficiency of uptake of elements; lettuce assimilated more than the other crops tested (barley, rape and ryegrass). Similarly, soil concentrations of the elements required to achieve toxic thresholds in plant tops increased in the order lettuce, ryegrass, rape and barley. Measurements made with conventional extractants of copper, nickel and zinc in soils can be of value in predicting plant uptake and hence toxicity, only if appropriate calibration curves plotting extractable soil metal against plant uptake are at hand for the particular soils and plants under consideration. Mild extracts are more sensitive to the soil properties, especially pH value, which determine plant uptake and results with metals in soil solution were promising, especially for zinc. Nevertheless, soil analyses for copper, nickel and zinc are not always closely associated with their likely toxicity to crops.     

Zn speciation in the organic horizon of a contaminated soil by micro-X-ray fluorescence, micro- and powder-EXAFS spectroscopy, and isotopic dilution

Soils that have been acutely contaminated by heavy metals show distinct characteristics, such as colonization by metal-tolerant plant species and topsoil enrichment in weakly degraded plant debris, because biodegradation processes are strongly inhibited by contamination. Such an organic topsoil, located downwind of an active zinc smelter and extremely rich in Zn (approximately 2%, dry weight), was investigated by X-ray diffraction, synchrotron-based X-ray microfluorescence, and powder- and micro-extended X-ray absorption fine structure (EXAFS) spectroscopy for Zn speciation and by isotopic dilution for Zn lability. EXAFS spectra recorded on size fractions and on selected spots of thin sections were analyzed by principal component analysis and linear combination fits. Although Zn primary minerals (franklinite, sphalerite, and willemite) are still present (approximately 15% of total Zn) in the bulk soil, Zn was found to be predominantly speciated as Zn-organic matter complexes (approximately 45%), outer-sphere complexes (approximately 20%), Zn-sorbed phosphate (approximately 10%), and Zn-sorbed iron oxyhydroxides (approximately 10%). The bioaccumulated Zn fraction is likely complexed to soil organic matter after the plants' death. The proportion of labile Zn ranges from 54 to 92%, depending on the soil fraction, in agreement with the high proportion of organically bound Zn. Despite its marked lability, Zn seems to be retained in the topsoil thanks to the huge content of organic matter, which confers to this horizon a high sorption capacity. The speciation of Zn in this organic soil horizon is compared with that found in other types of soils.     

Chemical speciation of dissolved Cu, Ni, and Co in a contaminated estuary in southwest Spain and its influence on plankton communities

Four surveys of the Huelva Estuary in southwest Spain and its sources, the Tinto and the Odiel Rivers, were carried out between 1996 and 1998. The surveys investigated the impact of metalliferous mining of sulfide-rich ores in the catchment area on metal speciation, metal concentrations in a macrophyte, and phytoplankton diversity and abundance. Chemical speciation measurements in the lower Tinto Estuary showed that metals were predominantly electrochemically labile (> 99% of total dissolved Cu, Co, and Ni at 10 microM Cu, 424 nM Co, and 500 nM Ni, S = 28). Concentrations of Cu complexing ligands and free cupric ions [Cu2+] in the Gulf of Cádiz ranged between 5.3 and 38 nM and 0.2-7.9 pM, respectively, with conditional stability constants of the ligands of log K'(CuL) = 11.7-12.6. At enhanced dissolved Cu concentrations in the lower Huelva Estuary, Cu complexing ligands were saturated with Cu, resulting in nanomolar [Cu2+], which increased upstream. Metal tissue concentrations of the macrophyte Blindingia marginata were high, and a clear relationship between dissolved labile Cu and macrophyte tissue Cu concentrations was observed. A low biodiversity was observed in the Huelva system (Shannon-Wiener indices (H) typically < 0.2). Nevertheless, the maximum biomass was observed in the lower Tinto Estuary, which showed high labile metal and nutrient concentrations and a low biodiversity (H < 0.02), thereby suggesting adaptation through evolutionary processes of the phytoplankton community to the harsh conditions.     

X-ray absorption and micro X-ray fluorescence spectroscopy investigation of copper and zinc speciation in biosolids

Despite its pivotal role in determining the risks and time frames associated with contaminant release, metal speciation remains a poorly understood aspect of biosolids chemistry. The work reported here used synchrotron-based spectroscopy techniques to investigate the speciation of copper and zinc in a range of Australian biosolids. High resolution element mapping of biosolids samples using micro X-ray fluorescence spectroscopy revealed considerable heterogeneity in key element associations, and a combination of both organic and inorganic copper and zinc binding environments. Linear combination fitting of K-edge X-ray absorption spectra indicated consistent differences in metal speciation between freshly produced and stockpiled biosolids. While sulfide minerals play a dominant role in metal binding in freshly dewatered biosolids, they are of lesser importance in dried biosolids that have been stockpiled. A degree of metal binding with iron oxide minerals was apparent but the results did not support the hypothesis that biosolids metals are chiefly associated with iron minerals. This work has potential implications for the long-term stability of metals in biosolids and their eventual fate following land application.     

Arsenic speciation in plankton organisms from contaminated lakes: transformations at the base of the freshwater food chain

The two complementary techniques high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) and X-ray absorption near edge structure (XANES) analysis were used to assess arsenic speciation in freshwater phytoplankton and zooplankton collected from arsenic-contaminated lakes in Yellowknife (Northwest Territories, Canada). Arsenic concentrations in lake water ranged from 7 μg L(-1) in a noncontaminated lake to 250 μg L(-1) in mine-contaminated lakes, which resulted in arsenic concentrations ranging from 7 to 340 mg kg(-1) d.w. in zooplankton organisms (Cyclops sp.) and from 154 to 894 mg kg(-1) d.w. in phytoplankton. The main arsenic compounds identified by HPLC-ICP-MS in all plankton were inorganic arsenic (from 38% to 98% of total arsenic). No other arsenic compounds were found in phytoplankton, but zooplankton organisms showed the presence of organoarsenic compounds, the most common being the sulfate arsenosugar, up to 47% of total arsenic, with traces of phosphate sugar, glycerol sugar, methylarsonate (MMA), and dimethylarsinate (DMA). In the uncontaminated Grace Lake, zooplankton also contained arsenobetaine (AB). XANES characterization of arsenic in the whole plankton samples showed As(V)-O as the only arsenic compound in phytoplankton, and As(III)-S and As(V)-O compounds as the two major inorganic arsenic species in zooplankton. The proportion of organoarsenicals and inorganic arsenic in zooplankton depends upon the arsenic concentration in lakes and shows the impact of arsenic contamination: zooplankton from uncontaminated lake has higher proportions of organoarsenic compounds and contains arsenobetaine, while zooplankton from contaminated area contains mostly inorganic arsenic.