Tammie L. Gerke

Speciation and distribution of vanadium in drinking water iron pipe corrosion by-products.

Vanadium (V) when ingested from drinking water in high concentrations (>15 μg L(-1)) is a potential health risk and is on track to becoming a regulated contaminant. High concentrations of V have been documented in lead corrosion by-products as Pb(5)(V(5+)O(4))(3)Cl (vanadinite) which, in natural deposits is associated with iron oxides/oxyhydroxides, phases common in iron pipe corrosion by-products. The extent of potential reservoirs of V in iron corrosion by-products, its speciation, and mechanism of inclusion however are unknown. The aim of this study is to assess these parameters in iron corrosion by-products, implementing synchrotron-based μ-XRF mapping and μ-XANES along with traditional physiochemical characterization. The morphologies, mineralogies, and chemistry of the samples studied are superficially similar to typical iron corrosion by-products. However, we found V present as discrete grains of Pb(5)(V(5+)O(4))(3)Cl likely embedded in the surface regions of the iron corrosion by-products. Concentrations of V observed in bulk XRF analysis ranged from 35 to 899 mg kg(-1). We calculate that even in pipes with iron corrosion by-products with low V concentration, 100 mg kg(-1), as little as 0.0027% of a 0.1-cm thick X 100-cm long section of that corrosion by-product needs to be disturbed to increase V concentrations in the drinking water at the tap to levels well above the 15 μg L(-1) notification level set by the State of California and could adversely impact human health. In addition, it is likely that large reservoirs of V are associated with iron corrosion by-products in unlined cast iron mains and service branches in numerous drinking water distribution systems.

Manganese deposition in drinking water distribution systems

This study provides a physicochemical assessment of manganese deposits on brass and lead components from two fully operational drinking water distributions systems. One of the systems was maintained with chlorine; the other, with secondary chloramine disinfection. Synchrotron-based in-situ micro X-ray adsorption near edge structure was used to assess the mineralogy. In-situ micro X-ray fluorescence mapping was used to demonstrate the spatial relationships between manganese and potentially toxic adsorbed metal ions. The Mn deposits ranged in thickness from 0.01 to 400 μm. They were composed primarily of Mn oxides/oxhydroxides, birnessite (Mn(3+) and Mn(4+)) and hollandite (Mn(2+) and Mn(4+)), and a Mn silicate, braunite (Mn(2+) and Mn(4+)), in varying proportions. Iron, chromium, and strontium, in addition to the alloying elements lead and copper, were co-located within manganese deposits. With the exception of iron, all are related to specific health issues and are of concern to the U.S. Environmental Protection Agency (U.S. EPA). The specific properties of Mn deposits, i.e., adsorption of metals ions, oxidation of metal ions and resuspension are discussed with respect to their influence on drinking water quality.

Changes in bacterial composition of biofilm in a metropolitan drinking water distribution system

This study examined the development of bacterial biofilms within a metropolitan distribution system. The distribution system is fed with different source water (i.e. groundwater, GW and surface water, SW) and undergoes different treatment processes in separate facilities.

Strontium Concentrations in Corrosion Products from Residential Drinking Water Distribution Systems

The United States Environmental Protection Agency (US EPA) will require some U.S. drinking water distribution systems (DWDS) to monitor nonradioactive strontium (Sr(2+)) in drinking water in 2013. Iron corrosion products from four DWDS were examined to assess the potential for Sr(2+) binding and release. Average Sr(2+) concentrations in the outermost layer of the corrosion products ranged from 3 to 54 mg kg(-1) and the Sr(2+) drinking water concentrations were all ≤0.3 mg L(-1). Micro-X-ray adsorption near edge structure spectroscopy and linear combination fitting determined that Sr(2+) was principally associated with CaCO3. Sr(2+) was also detected as a surface complex associated with α-FeOOH. Iron particulates deposited on a filter inside a home had an average Sr(2+) concentration of 40.3 mg kg(-1) and the associated drinking water at a tap was 210 μg L(-1). The data suggest that elevated Sr(2+) concentrations may be associated with iron corrosion products that, if disturbed, could increase Sr(2+) concentrations above the 0.3 μg L(-1) US EPA reporting threshold. Disassociation of very small particulates could result in drinking water Sr(2+) concentrations that exceed the US EPA health reference limit (4.20 mg kg(-1) body weight).

Enrichment of SiO2 in rhyolites by fractional crystallization: An experimental study of peraluminous granitic rocks from the St. Francois Mountains, Missouri, USA

Abstract Experiments were conducted to test the hypothesis that higher silica rhyolites of the St. Francois Mountains, Missouri, USA are products of fractional crystallization of lower silica granitic magmas. Experiments were carried out at pressures of 0.5 and 1.0 kb under water-saturated conditions, temperatures ranged from 800° to 925°C and the oxygen fugacity for all experiments were maintained at, or near, the nickel-nickel oxide (NNO) buffer level. Results of experiments with Butler Hill granite indicate that fractionation of near liquidus silicate phases, orthopyroxene and plagioclase, causes an enrichment of SiO 2 in the residual melts. Mineralogical and chemical compositions of the experimental charges are similar to that of higher silica Grassy Mountain rhyolites of the St. Francois Mountains. Experiments also show that at pressures of 1.0 Kb or higher orthopyroxene reacts with the hydrous melt to produce biotite which is a common phase in the plutonic rocks of the St. Francois Mountains.

Development of an Escherichia coli K12-specific quantitative polymerase chain reaction assay and DNA isolation suited to biofilms associated with iron drinking water pipe corrosion products.

A quantitative polymerase chain reaction assay (115 bp amplicon) specific to Escherichia coli K12 with an ABI(TM) internal control was developed based on sequence data encoding the rfb gene cluster. Assay specificity was evaluated using three E. coli K12 strains (ATCC W3110, MG1655 & DH1), 24 non-K12 E. coli and 23 bacterial genera. The biofilm detection limit was 10(3) colony-forming units (CFU) E. coli K12 mL(-1), but required a modified protocol, which included a bio-blocker Pseudomonas aeruginosa with ethylenediaminetetraacetic acid buffered to pH 5 prior to cell lysis/DNA extraction. The novel protocol yielded the same sensitivity for drinking water biofilms associated with Fe3O4 (magnetite)-coated SiO2 (quartz) grains and biofilm-surface iron corrosion products from a drinking water distribution system. The novel DNA extraction protocol and specific E. coli K12 assay are sensitive and robust enough for detection and quantification within iron drinking water pipe biofilms, and are particularly well suited for studying enteric bacterial interactions within biofilms.

Sourcing Volcanic Millstones from Greco-Roman Sites in Albania

Abstract Provenience studies provide insights concerning trade in various goods, such as millstones. This is the first attempt to source millstones from Albania. Thirty-one vesicular volcanic millstones, predominately from the Greek and Roman periods, were obtained from two sites, 21 from Apollonia and ten from Butrint. The purpose of this study was to determine the provenience of these millstones using textural, mineralogical, and chemical data. The compositions of the samples were compared to those of vesicular volcanic sources in the central and eastern Mediterranean. Eight viable sources were initially identified based on major element chemistry; these were ultimately reduced to three based on trace element provenience studies. All of the Apollonia and five of the Butrint millstones have chemical signatures similar to those of Sicilian sources (the Iblean Fields and Mt. Etna). The remaining five Butrint millstones are chemically similar to stones from quarries other on the Cycladic island of Melos other than Rema (another Melian quarry), suggesting that Melian sources were exploited earlier than previously thought. The results of this preliminary study indicate there was no preference for a given source region at a particular time in the past. They also provide a baseline for future provenience studies of millstone trade patterns in Albania.

The Relationship Between Iron Oxides/Oxyhydroxides and Toxic Metal Ions in Drinking Water Distribution Systems—A Review

Iron (Fe) oxides/oxyhydroxides in drinking water distribution systems (DWDS), produced by electrochemical, chemical, and biological reactions, can adsorb toxic metal ions, including strontium, lead, arsenic, and vanadium that, if desorbed, generate pulses of drinking water with elevated toxic metal ion concentrations. To illustrate that potential, sorption data for strontium (cation) and vanadium (oxyanion) in functioning DWDS are reviewed. In addition, the influence of flow/no flow on adsorption and desorption of strontium in a model DWDS is included. The reactions that influence adsorption and desorption within a DWDS are extremely complicated and poorly understood. The sorption capacity of Fe oxhydroxides varies with surface area, which in turn varies with source water and disinfectant. Desorption and release can be triggered by changes in source water, disinfection chemicals, or flow. Because of the interrelatedness of adsorption/desorption and Fe corrosion products, subtle changes in DWDS operating p...