Advanced in situ spectroscopic techniques and their applications in environmental biogeochemistry: introduction to the special section

Understanding the molecular-scale complexities and interplay of chemical and biological processes of contaminants at solid, liquid, and gas interfaces is a fundamental and crucial element to enhance our understanding of anthropogenic environmental impacts. The ability to describe the complexity of environmental biogeochemical reaction mechanisms relies on our analytical ability through the application and developmemnt of advanced spectroscopic techniques. Accompanying this introductory article are nine papers that either review advanced in situ spectroscopic methods or present original research utilizing these techniques. This collection of articles summarizes the challenges facing environmental biogeochemistry, highlights the recent advances and scientific gaps, and provides an outlook into future research that may benefit from the use of in situ spectroscopic approaches. The use of synchrotron-based techniques and other methods are discussed in detail, as is the importance to integrate multiple analytical approaches to confirm results of complementary procedures or to fill data gaps. We also argue that future direction in research will be driven, in addition to recent analytical developments, by emerging factors such as the need for risk assessment of new materials (i.e., nanotechnologies) and the realization that biogeochemical processes need to be investigated in situ under environmentally relevant conditions.     

Spectroscopic speciation and quantification of lead in phosphate-amended soils

The immobilization of Pb in contaminated soils as pyromorphite [Pb(5)(PO(4))(3)Cl, OH, F] through the addition of various phosphate amendments has gained much attention in the remediation community. However, it is difficult to fully determine the speciation and amount of soil Pb converted to pyromorphite by previously employed methods, such as selective sequential extraction procedures and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy, which often lead to erroneous results in these non-equilibrated and heterogeneous systems. Statistical analysis by linear combination fitting (LCF) applied to X-ray absorption fine structure (XAFS) spectroscopic data of Pb-contaminated soil samples relative to known Pb reference material provides direct, in situ evidence of dominate Pb species in the amended soils without chemical or physical disruption to the Pb species as well as a weighted quantification output. The LCF-XAFS approach illustrated that pyromorphite concentration ranged from 0% (control soil) to 45% (1% phosphoric acid amendment, residence time of 32 mo) relative to the total Pb concentration. The Pb speciation in the nonamended control soil included Pb-sulfur species (galena + angelsite = 53%), adsorbed Pb (inner-sphere + outer-sphere + organic-bound = 45%), and Pb-carbonate phases (cerussite + hydrocerussite = 2%). The addition of P promoted pyromorphite formation and the rate of formation increased with increasing P concentration (up to 45%). The supplemental addition of an iron amendment as an iron-rich byproduct with triple superphosphate (TSP) enhanced pyromorphite formation relative to independent TSP amendment of like concentrations (41 versus 29%). However, the amendment of biosolids and biosolids plus TSP observed little pyromorphite formation (1-16% of total Pb), but a significant increase of sorbed Pb was determined by LCF-XAFS.     

Evidence for struvite in poultry litter: effect of storage and drying

The use of spectroscopic techniques (especially phosphorus-31 nuclear magnetic resonance [(31)P-NMR] and X-ray absorption near edge structure spectroscopy) has recently advanced the analysis of the speciation of P in poultry litter (PL) and greatly enhanced our understanding of changes in P pools in PL that receive alum (aluminum sulfate) to reduce water-soluble P and control ammonia emissions from poultry houses. Questions remain concerning changes of P species during long-term storage, drying, or after application of PL to cropland or for other uses, such as turfgrass. In this study, we investigated a set of six PL samples (of which three were alum-amended and three were unamended) that had been characterized previously. The P speciation was analyzed using solid-state (31)P-NMR spectroscopy, and the mineralogy was analyzed by powder X-ray diffraction (XRD) after storing the samples moist and dried for up to 5 yr under controlled conditions. The magnesium ammonium phosphate mineral struvite was identified in all but one PL samples. Struvite concentrations were generally lower in dried samples (< or = 14%) than in samples stored moist (23 and 26%). The moist samples also had higher concentrations of phosphate bound to aluminum hydroxides. Solid-state NMR spectroscopy was in general more sensitive than XRD in detecting and quantifying P species. Although phosphate associated with calcium and aluminum made up a large proportion of P species, they were not detected by XRD.     

A methodology for evaluating environmental planning systems: A case study of Canada

Sustainable environmental management is contingent on having an effective environmental planning system. A new methodology for designing and evaluating environmental planning systems is described and applied to a case study evaluation of the Canadian environmental planning process. The methodology is based on eight international best practice principles for environmental planning and 45 indicators. The research illustrates the benefits of the evaluation methodology in identifying how to improve environmental planning systems to achieve desired results. The methodology is applicable to a wide variety of jurisdictions.     

Determination of dominant biogeochemical processes in a contaminated aquifer-wetland system using multivariate statistical analysis

Determining the processes governing aqueous biogeochemistry in a wetland hydrologically linked to an underlying contaminated aquifer is challenging due to the complex exchange between the systems and their distinct responses to changes in precipitation, recharge, and biological activities. To evaluate temporal and spatial processes in the wetland-aquifer system, water samples were collected using cm-scale multi-chambered passive diffusion samplers (peepers) to span the wetland-aquifer interface over a period of 3 yr. Samples were analyzed for major cations and anions, methane, and a suite of organic acids resulting in a large dataset of over 8000 points, which was evaluated using multivariate statistics. Principal component analysis (PCA) was chosen with the purpose of exploring the sources of variation in the dataset to expose related variables and provide insight into the biogeochemical processes that control the water chemistry of the system. Factor scores computed from PCA were mapped by date and depth. Patterns observed suggest that (i) fermentation is the process controlling the greatest variability in the dataset and it peaks in May; (ii) iron and sulfate reduction were the dominant terminal electron-accepting processes in the system and were associated with fermentation but had more complex seasonal variability than fermentation; (iii) methanogenesis was also important and associated with bacterial utilization of minerals as a source of electron acceptors (e.g., barite BaSO(4)); and (iv) seasonal hydrological patterns (wet and dry periods) control the availability of electron acceptors through the reoxidation of reduced iron-sulfur species enhancing iron and sulfate reduction.     

Assessing and improving management practices when planning packaging waste collection systems

Packaging waste collection systems are responsible to collect, within a geographic area, three types of packaging materials (paper, glass and plastic/metal) that are disposed by the final consumer into special bins. Those systems are often characterized by having a network with multiple depots that act as transfer and sorting stations, and where the vehicle fleet is based. However, each depot is often managed independently and not as a part of a unique system. In this work, four current tactical/operational practices that contribute to the independent management of each depot are analysed. The change of such practices is investigated and their impact assessed on the total collection cost. A solution methodology based on mathematical formulations is developed to plan service areas, vehicle routes and vehicle schedules taking into account new alternative solutions in managing the system as a whole. Such methodology is applied to a real case study of a company responsible for the collection of the packaging waste in 7 municipalities in mainland Portugal. New service areas, collection routes and vehicle schedules are defined and significant savings are obtained in terms of the total distance travelled as well as in terms of the number of required vehicles, resulting in a decreasing of the total system cost.     

Effects of particle size on chemical speciation and bioavailability of copper to earthworms (Eisenia fetida) exposed to copper nanoparticles

To investigate the role of particle size on the oxidation, bioavailability, and adverse effects of manufactured Cu nanoparticles (NPs) in soils, we exposed the earthworm Eisenia ferida to a series of concentrations of commercially produced NPs labeled as 20- to 40-nm or < 100-nm Cu in artificial soil media. Effects on growth, mortality, reproduction, and expression of a variety of genes associated with metal homeostasis, general stress, and oxidative stress were measured. We also used X-ray absorption spectroscopy and scanning X-ray fluorescence microscopy to characterize changes in chemical speciation and spatial distribution of the NPs in soil media and earthworm tissues. Exposure concentrations of Cu NPs up to 65 mg kg(-1) caused no adverse effects on ecologically relevant endpoints. Increases in metallothionein expression occurred at concentrations exceeding 20 mg kg(-1) of Cu NPs and concentrations exceeding 10 mg kg(-1) of CuSO4. Based on the relationship of Cu tissue concentration to metallothionein expression level and the spatial distribution and chemical speciation of Cu in the tissues, we conclude that Cu ions and oxidized Cu NPs were taken up by the earthworms. This study suggests that oxidized Cu NPs may enter food chains from soil but that adverse effects in earthworms are likely to occur only at relatively high concentrations (> 65 mg Cu kg(-1) soil).     

QUANTIFICATION OF ACTINIDE MIGRATION PATHWAYS AT ROCKY FLATS,COLORADO1

ABSTRACT: Migration of plutonium, americium, and uranium (actinides) in the environment at the Rocky Flats Environmental Technology Site (RFETS) is the subject of ongoing studies to develop effective strategies for cleanup and regulatory closure of the Department of Energy facility. The Actinide Migration Evaluation pathway analysis quantified actinide transport processes to validate a qualitative conceptual model of environmental actinide transport. Major actinide transport mechanisms evaluated include surface water, ground water, airborne, and biological pathways. Relative quantities of actinide movement via different pathways were compared in terms of actinide loads delivered off the RFETS, using a combination of monitoring data, predictive transport models and results from historic RFETS studies. Results indicate air and surface water constitute the dominant transport mechanisms for plutonium and americium. In ground water, shallow alluvial flow is a limited pathway for plutonium and americium because of the low aqueous solubility of these actinides and their tendency to sorb to soil. However, localized flow in shallow alluvium is a more significant pathway for uranium movement, because of the relatively higher solubility of uranium (VI) species, though isotopic ratios indicate much of the uranium is from natural sources. Biological transport of actinides by mammals, birds, fish, and arthropods is small compared to the other pathways.     

Geochemical parameters influencing tungsten mobility in soils

The biogeochemistry of tungsten and its effects on mobility have recently gained attention due to the existence of human cancer clusters, such as in Fallon, NV. Tungsten exists in many environmental matrices as the soluble and mobile tungstate anion. However, tungsten can polymerize with itself and other anions, creating poly- and heteropoly-tungstates with variable geochemical and toxicological properties. In the present work, geochemical parameters are determined for tungstate species in a model soil that describe the potential for tungsten mobility. Soluble tungsten leached from a metallic tungsten-spiked soil after six to twelve months aging reached an equilibrium concentration >150 mg/L within 4 h of extraction with deionized water. Partition coefficients determined for various tungstate and polytungstate compounds in the model soil suggest a dynamic system in which speciation changes over time affect tungsten geochemical behavior. Partition coefficients for tungstate and some poly-species have been observed to increase by a factor of 3 to 6 over a four month period, indicating decreased mobility with soil aging.     

XANES spectroscopic analysis of phosphorus speciation in alum-amended poultry litter

Aluminum sulfate (alum; Al(2)(SO(4))(3).14H(2)O) is used as a chemical treatment of poultry litter to reduce the solubility and release of phosphate, thereby minimizing the impacts on adjacent aquatic ecosystems when poultry litter is land applied as a crop fertilizer. The objective of this study was to determine, through the use of X-ray absorption near edge structure (XANES) spectroscopy and sequential extraction, how alum amendments alter P distribution and solid-state speciation within the poultry litter system. Our results indicate that traditional sequential fractionation procedures may not account for variability in P speciation in heterogeneous animal manures. Analysis shows that NaOH-extracted P in alum amended litters is predominantly organic ( approximately 80%), whereas in the control samples, >60% of NaOH-extracted P was inorganic P. Linear least squares fitting (LLSF) analysis of spectra collected of sequentially extracted litters showed that the P is present in inorganic (P sorbed on Al oxides, calcium phosphates) and organic forms (phytic acid, polyphosphates, and monoesters) in alum- and non-alum-amended poultry litter. When determining land application rates of poultry litter, all of these compounds must be considered, especially organic P. Results of the sequential extractions in conjunction with LLSF suggest that no P species is completely removed by a single extractant. Rather, there is a continuum of removal as extractant strength increases. Overall, alum-amended litters exhibited higher proportions of Al-bound P species and phytic acid, whereas untreated samples contained Ca-P minerals and organic P compounds. This study provides in situ information about P speciation in the poultry litter solid and about P availability in alum- and non-alum-treated poultry litter that will dictate P losses to ground and surface water systems.     

系统动力学在我国可持续发展战略中的研究进展

系统动力学是一种以反馈控制理论为基础、计算机仿真技术为手段，研究复杂社会经济大系统的方法。随着可持续发展战略的提出，该方法得到了广泛应用。综述了近年来系统动力学方法在我国可持续发展战略中的研究进展，着重介绍了该方法在区域资源生态承载力方面的研究，提出了系统动力学研究的方向。     

Relationship between metal speciation in soil solution and metal adsorption at the root surface of ryegrass

The total metal content of the soil or total metal concentration in the soil solution is not always a good indicator for metal availability to plants. Therefore, several speciation techniques have been developed that measure a defined fraction of the total metal concentration in the soil solution. In this study the Donnan Membrane Technique (DMT) was used to measure free metal ion concentrations in CaCl(2) extractions (to mimic the soil solution, and to work under standardized conditions) of 10 different soils, whereas diffusive gradients in thin-films (DGT) and scanning chronopotentiometry (SCP) were used to measure the sum of free and labile metal concentrations in the CaCl(2) extracts. The DGT device was also exposed directly to the (wetted) soil (soil-DGT). The metal concentrations measured with the speciation techniques are related to the metal adsorption at the root surface of ryegrass (Lolium perenne L.), to be able to subsequently predict metal uptake. In most cases the metal adsorption related pH-dependently to the metal concentrations measured by DMT, SCP, and DGT in the CaCl(2) extract. However, the relationship between metal adsorption at the root surface and the metal concentrations measured by the soil-DGT was not-or only slightly-pH dependent. The correlations between metal adsorption at the root surface and metal speciation detected by different speciation techniques allow discussion about rate limiting steps in biouptake and the contribution of metal complexes to metal bioavailability.     

Developing the interaction matrix technique as a tool assessing the impact of traffic on air quality

This paper develops a technique which can be used as a preliminary tool for assessing air quality related to urban traffic. It combines a Geographic Information System (GIS) with an interaction matrix-type methodology based on a system analysis approach. The matrix identifies and quantifies interactions between all selected variables involved in a system as well as their interaction with the system as a whole. This matrix is used to determine the weightings to apply to spatial datasets within a GIS to develop a pollution vulnerability map. The focus of the paper is to introduce and assess a more versatile coding of the interaction matrix with respect to previously used coding. A case study is presented in which the modified interaction methodology is applied to data for a busy urban location. The resulting vulnerability map, in terms of pollution vulnerable hot spots, was compared to a pollution map derived from an advanced dispersion model. The interaction matrix technique with GIS can be used as a tool complementary to sophisticated numerical modelling and has potential as an analytical tool to evaluate multidisciplinary systems.     

Vertical distribution and speciation of trace metals in weathering flotation residues of a zinc/lead sulfide mine

Sulfide-bearing mine tailings are a serious environmental problem around the world. In this study, the vertical distribution and speciation of Zn and Pb in the fine-grained flotation residues of a former sulfide ore mine in Germany were investigated to assess the inorganic weathering processes that effect the environmental risk arising from this site. Total metal contents were determined by X-ray fluorescence spectroscopy (XRF). Mobilizable fractions of Zn, Pb, Fe, and Mn were quantified by sequential chemical extractions (SCE). Furthermore, the speciation of Zn was analyzed by Zn K-edge extended X-ray absorption fine structure spectroscopy (EXAFS) to identify the residual Zn species. The variations in pH and inorganic C content show an acidification of the topsoil to pH 5.5. EXAFS results confirm that Zn is mainly bound in sphalerite in the subsoil and weathering reactions lead to a redistribution of Zn in the topsoil. A loss of 35% Zn and S from the topsoil compared with the parent material with 10 g kg-1 Zn and neutral pH has been observed. If acidification proceeds it will lead to a significant release of Zn, S, and Pb to the ground water. In contrast to Zn, Pb is enriched in the mobile fraction of the topsoil by more than a factor of two compared with the subsoil which contains a total of 2 g kg-1 Pb. Thus, the high bioavailability of Pb and the potential for Pb uptake by plants and animals currently represent the most severe threat for environmental health.     

Combined application of QEM-SEM and hard X-ray microscopy to determine mineralogical associations and chemical speciation of trace metals

We describe the application of quantitative evaluation of mineralogy by scanning electron microscopy in combination with techniques commonly available at hard X-ray microprobes to define the mineralogical environment of a bauxite residue core segment with the more specific aim of determining the speciation of trace metals (e.g., Ti, V, Cr, and Mn) within the mineral matrix. Successful trace metal speciation in heterogeneous matrices, such as those encountered in soils or mineral residues, relies on a combination of techniques including spectroscopy, microscopy, diffraction, and wet chemical and physical experiments. Of substantial interest is the ability to define the mineralogy of a sample to infer redox behavior, pH buffering, and mineral-water interfaces that are likely to interact with trace metals through adsorption, coprecipitation, dissolution, or electron transfer reactions. Quantitative evaluation of mineralogy by scanning electron microscopy coupled with micro-focused X-ray diffraction, micro-X-ray fluorescence, and micro-X-ray absorption near edge structure (mXANES) spectroscopy provided detailed insights into the composition of mineral assemblages and their effect on trace metal speciation during this investigation. In the sample investigated, titanium occurs as poorly ordered ilmenite, as rutile, and is substituted in iron oxides. Manganese's spatial correlation to Ti is closely linked to ilmenite, where it appears to substitute for Fe and Ti in the ilmenite structure based on its mXANES signature. Vanadium is associated with ilmenite and goethite but always assumes the +4 oxidation state, whereas chromium is predominantly in the +3 oxidation state and solely associated with iron oxides (goethite and hematite) and appears to substitute for Fe in the goethite structure.     

X-ray microspectroscopy and chemical reactions in soil microsites

Soils provide long-term storage of environmental contaminants, which helps to protect water and air quality and diminishes negative impacts of contaminants on human and ecosystem health. Characterizing solid-phase chemical species in highly complex matrices is essential for developing principles that can be broadly applied to the wide range of notoriously heterogeneous soils occurring at the earth's surface. In the context of historical developments in soil analytical techniques, we describe applications of bulk-sample and spatially resolved synchrotron X-ray absorption spectroscopy (XAS) for characterizing chemical species of contaminants in soils, and for determining the uniqueness of trace-element reactivity in different soil microsites. Spatially resolved X-ray techniques provide opportunities for following chemical changes within soil microsites that serve as highly localized chemical micro- (or nano-)reactors of unique composition. An example of this microreactor concept is shown for micro-X-ray absorption near edge structure analysis of metal sulfide oxidation in a contaminated soil. One research challenge is to use information and principles developed from microscale soil chemistry for predicting macroscale and field-scale behavior of soil contaminants.     

Characterization of phosphorus species in biosolids and manures using XANES spectroscopy

Identification of the chemical P species in biosolids or manures will improve our understanding of the long-term potential for P loss when these materials are land applied. The objectives of this study were to determine the P species in dairy manures, poultry litters, and biosolids using X-ray absorption near-edge structure (XANES) spectroscopy and to determine if chemical fractionation techniques can provide useful information when interpreted based on the results of more definitive P speciation studies. Our XANES fitting results indicated that the predominant forms of P in organic P sources included hydroxylapatite, PO(4) sorbed to Al hydroxides, and phytic acid in lime-stabilized biosolids and manures; hydroxylapatite, PO(4) sorbed on ferrihydrite, and phytic acid in lime- and Fe-treated biosolids; and PO(4) sorbed on ferrihydrite, hydroxylapatite, beta-tricalcium phosphate (beta-TCP), and often PO(4) sorbed to Al hydroxides in Fe-treated and digested biosolids. Strong relationships existed between the proportions of XANES PO(4) sorbed to Al hydroxides and NH(4)Cl- + NH(4)F-extractable P, XANES PO(4) sorbed to ferrihydrite + phytic acid and NaOH-extractable P, and XANES hydroxylapatite + beta-TCP and dithionite-citrate-bicarbonate (DCB)- + H(2)SO(4)-extractable P (r(2) = 0.67 [P = 0.01], 0.78 [P = 0.01], and 0.89 [P = 0.001], respectively). Our XANES fitting results can be used to make predictions about long-term solubility of P when biosolids and manures are land applied. Fractionation techniques indicate that there are differences in the forms of P in these materials but should be interpreted based on P speciation data obtained using more advanced analytical tools.     

A methodology for estimation of vehicle emissions in an urban environment: an example from Greater Manchester

Road transport is a major contributor to urban air pollution. The introduction of local air qua lity management in the UK will require objective test procedures to evaluate and prioritise the air pollution benefits of existing transport systems and proposed developments. This methodology has been developed to assist the land use and transport planning professionals in evaluating current and potential future impacts on air quality. The method couples an emissions estimation procedure to a traffic flow database. It requires data on emission factors, the composition of the vehicle fleet, vehicle control technologies and the daily traffic flow profile. With these data, it is possible to generate emission estimates per kilometre, link or road as selected by the user. Forecasts can be made by varying input variables. The current methodology allows prediction of five or more pollutant species/classes, limited only by availability of emission factors. The method utilises a commercially available personal computer based spreadsheet. Further coupling of the method to a geographical information system will improve the decision support capability of the method.     

Prediction of metal-adsorption behaviour in the remediation of water contamination using indigenous microorganisms

In recent years, the adsorption of heavy metal cations onto bacterial surfaces has been studied extensively. This paper reports the findings of a study conducted on the heavy metal ions found in mine effluents from a mining plant where Co²⁺ and Ni²⁺ bearing minerals are processed. Heavy metal ions are reported to be occasionally present in these mine effluents, and the proposed microbial sorption technique offers an acceptable solution for the removal of these heavy metals. The sorption affinity of microorganisms for metal ions can be used to select a suitable microbial sorbent for any particular bioremediation process. Interactions of heavy metal ions (Co²⁺ and Ni²⁺) and light metal ions (Mg²⁺ and Ca²⁺) with indigenous microbial cells (Brevundimonas spp., Bacillaceae bacteria and Pseudomonas aeruginosa) were investigated using the Langmuir adsorption isotherm, pseudo second-order reaction kinetics model and a binary-metal system. Equilibrium constants and adsorption capacities derived from these models allowed delineation of the effect of binding affinity and metal concentration ratios on the overall adsorption behaviour of microbial sorbents, as well as prediction of performance in bioremediation systems. Although microbial sorbents used in this study preferentially bind to heavy metal ions, it was observed that higher concentrations (>90 mg/?) of light metal ions in multi-metal solutions inhibit the adsorption of heavy metal ions to the bacterial cell wall. However, the microbial sorbents reduced Ni²⁺ levels in the mine-water used (93–100% Ni²⁺ removal) to below the maximum acceptable limit of 350 μg/?, established by the South African Bureau of Standards. Competition among metal ions for binding sites on the biomaterial surface can occur during the bioremediation process, but microbial sorption affinity for heavy metal ions can enhance their remediation in dilute (<5 mg/? heavy metal) wastewaters.     

Effects of sedimentation on soil nutrient dynamics in riparian forests

The influence of sedimentation rates on biogeochemistry of riparian forests was studied near ephemeral streams at Fort Benning, GA. Upper reaches of seven ephemeral streams had received varying rates of sedimentation stemming from erosion along unpaved roadways at the military installation. Two reference catchments were also included in the study. Decomposition of foliar litter, microbial C and N, N mineralization, and arthropod populations were compared within and among catchments. Rates of sedimentation over the past 25 yr ranged from 0 in references to 4.0 cm yr(-1). Decomposition rates declined exponentially with sedimentation rates as low as 0.20 to 0.32 cm yr(-1) and appeared to reach an equilibrium at a sedimentation rate of 0.5 cm yr(-1). Nitrogen mineralization and microbial C and N followed the same trend. Sedimentation had no discernible effect on arthropod populations. These data suggest that biogeochemical cycles may be altered by sedimentation rates that commonly occur in some floodplain forests.