Characterization of metals released from coal fly ash during dredging at the Kingston ash recovery project.

A storage-pond dike failure occurred on December 22, 2008 at the Tennessee Valley Authority Kingston Fossil Plant resulting in the release of over 4million cubic meters (5million cubic yards) of fly ash. Approximately half of the released ash was deposited in the main channel of the Emory River, Tennessee, USA. Remediation efforts of the Emory River focused on hydraulic dredging, as well as mechanical excavation in targeted areas. However, agitation of the submerged fly ash during hydraulic dredging introduces river water into the fly ash material, which could promote dissolution and desorption of metals from the solid fly ash material. Furthermore, aeration of the dredge slurry could alter the redox state of metals in the fly ash material and thereby change their sorption, mobility, and toxicity properties. The research presented here focuses on the concentrations and speciation of metals during the fly ash recovery from the Emory River. Our results indicate that arsenite [As(III)] released from the fly ash material during dredging was slowly oxidized to arsenate [As(V)] in the slurry recovery system with subsequent removal through precipitation or sorption reactions with suspended fly ash material. Concentrations of other dissolved metals, including iron and manganese, also generally decreased in the ash recovery system prior to water discharge back to the river.

Comparison of on-line detectors for field flow fractionation analysis of nanomaterials.

Characterization of nanomaterials must include analysis of both size and chemical composition. Many analytical techniques, such as dynamic light scattering (DLS), are capable of measuring the size of suspended nanometer-sized particles, yet provide no information on the composition of the particle. While field flow fractionation (FFF) is a powerful nanoparticle sizing technique, common detectors used in conjunction with the size separation, including UV, light-scattering, and fluorescence spectroscopy, do not provide the needed particle compositional information. Further, these detectors do not respond directly to the mass concentration of nanoparticles. The present work describes the advantages achieved when interfacing sensitive and elemental specific detectors, such as inductively coupled plasma atomic emission spectroscopy and mass spectrometry, to FFF separation analysis to provide high resolution nanoparticle sizing and compositional analysis at the µg/L concentration level, a detection at least 10-100-fold lower than DLS or FFF-UV techniques. The full benefits are only achieved by utilization of all detector capabilities, such as dynamic reaction cell (DRC) ICP-MS. Such low-level detection and characterization capability is critical to nanomaterial investigations at biologically and environmentally relevant concentrations. The techniques have been modified and applied to characterization of all four elemental constituents of cadmium selenide-zinc sulfide core-shell quantum dots, and silver nanoparticles with gold seed cores. Additionally, sulfide coatings on silver nanoparticles can be detected as a potential means to determine environmental aging of nanoparticles.

Characterization of silver nanoparticles using flow-field flow fractionation interfaced to inductively coupled plasma mass spectrometry.

The ability to detect and identify the physiochemical form of contaminants in the environment is important for degradation, fate and transport, and toxicity studies. This is particularly true of nanomaterials that exist as discrete particles rather than dissolved or sorbed contaminant molecules in the environment. Nanoparticles will tend to agglomerate or dissolve, based on solution chemistry, which will drastically affect their environmental properties. The current study investigates the use of field flow fractionation (FFF) interfaced to inductively coupled plasma-mass spectrometry (ICP-MS) as a sensitive and selective method for detection and characterization of silver nanoparticles. Transmission electron microscopy (TEM) is used to verify the morphology and primary particle size and size distribution of precisely engineered silver nanoparticles. Subsequently, the hydrodynamic size measurements by FFF are compared to dynamic light scattering (DLS) to verify the accuracy of the size determination. Additionally, the sensitivity of the ICP-MS detector is demonstrated by fractionation of µg/L concentrations of mixed silver nanoparticle standards. The technique has been applied to nanoparticle suspensions prior to use in toxicity studies, and post-exposure biological tissue analysis. Silver nanoparticles extracted from tissues of the sediment-dwelling, freshwater oligochaete Lumbriculus variegatus increased in size from approximately 31-46nm, indicating a significant change in the nanoparticle characteristics during exposure.

Geochemical investigations of metals release from submerged coal fly ash using extended elutriate tests.

A storage pond dike failure occurred at the Tennessee Valley Authority Kingston Fossil Plant that resulted in the release of over 3.8 million cubic meters (5 million cubic yards) of fly ash. Approximately half of this material deposited in the main channel of the Emory River, 3.5 km upstream of the confluence of the Emory and Clinch Rivers, Tennessee, USA. Remediation efforts to date have focused on targeted removal of material from the channel through hydraulic dredging, as well as mechanical excavation in some areas. The agitation of the submerged fly ash during hydraulic dredging introduces river water into the fly ash material, which could alter the redox state of metals present in the fly ash and thereby change their sorption and mobility properties. A series of extended elutriate tests were used to determine the concentration and speciation of metals released from fly ash. Results indicated that arsenic and selenium species released from the fly ash materials during elutriate preparation were redox stable over the course of 10d, with dissolved arsenic being present as arsenate, and dissolved selenium being present as selenite. Concentrations of certain metals, such as arsenic, selenium, vanadium, and barium, increased in the elutriate waters over the 10d study, whereas manganese concentrations decreased, likely due to oxidation and precipitation reactions.

Alcohol consumption, cigarette smoking and risk of subtypes of oesophageal and gastric cancer: a prospective cohort study.

OBJECTIVE: Alcohol consumption and cigarette smoking may be differentially associated with oesophageal squamous cell carcinoma (OSCC), oesophageal adenocarcinoma (OAC), gastric cardia adenocarcinoma (GCA) and gastric non-cardia adenocarcinoma (GNCA). However, because this was based on retrospective studies, these hypotheses were examined in a prospective cohort. METHODS: The prospective Netherlands Cohort Study consists of 120 852 participants who completed a baseline questionnaire on diet and other cancer risk factors in 1986. After 16.3 years of follow-up, 107 OSCC, 145 OAC, 164 GCA and 491 GNCA cases were available for analysis using Cox proportional hazards models and the case-cohort approach. RESULTS: The multivariable adjusted incidence rate ratio (RR) for OSCC was 4.61 (95% CI 2.24 to 9.50) for > or = 30 g ethanol/day compared with abstainers (p trend <0.001), while no associations with alcohol were found for OAC, GCA or GNCA. Compared with never smokers, current smokers had RRs varying from 1.60 for GCA to 2.63 for OSCC, and were statistically significant or borderline statistically significant. Frequency, duration and pack-years of smoking were independently associated with risk of all four cancers. A positive interaction was found between alcohol consumption and smoking status regarding OSCC risk. The RR for current smokers who consumed >15 g/day of ethanol was 8.05 (95% CI 3.89 to 16.60; p interaction = 0.65), when compared with never smokers who consumed <5 g/day of ethanol. CONCLUSIONS: This prospective study found alcohol consumption to be associated with increased risk of only OSCC. Cigarette smoking was associated with risk of all four cancers.

Tea and coffee drinking and ovarian cancer risk: results from the Netherlands Cohort Study and a meta-analysis.

In a cohort study, ovarian cancer (280 cases) showed no significant association with tea or coffee, the multivariable rate ratios being 0.94 (95% confidence interval (CI): 0.89, 1.00) and 1.04 (95% CI: 0.97, 1.12) per cup per day, respectively. A meta-analysis also produced no significant findings overall, though the cohort studies showed a significant inverse association for tea.

Automated storage of gas chromatography-mass spectrometry data in a relational database to facilitate compound screening and identification.

This paper describes a database containing massspectra from gas chromatography-mass spectrometry(GC-MS) measurements as a tool for easy screening for multiple compounds. In this way additional compounds can be reported from the same run together with routine pesticide monitoring with little effort. The relevant analytical data from the GC-MS measurements are transferred automatically to a database. Search algorithms in the database, containing the US EPA and Dutch NEN GC-MS identification criteria as standard settings, are used to identify compounds in the data. Screening of samples analysed in our laboratory show the ubiquitous presence of--up until now in monitoring largely overlooked--compounds in surface waters in The Netherlands. Most frequently found compounds include TAED (complexing agent), 2-methyl quinoline (industrial solvent), atrazin and desethylatrazin (pesticide and degradation product), caffeine (human consumption), surfinol-104 (anti foaming agent), HHCB (Galaxolide) and AHTN (Tonalide; fragrances). The database can also be used to quickly search a large number of datafiles for rare contaminants. This way, some interesting compounds such as pentoxifilin (a pharmaceutical) and Irgarol 1051 (an antifouling compound) were found.

Mercury in sediment and fish from North Mississippi Lakes.

Sediments and/or fish were collected from Sardis, Enid and Grenada Lakes, which are located in three different watersheds in North Mississippi, in order to assess mercury contamination. The mean total mercury concentration in sediments from Enid Lake in 1997 was 0.154 mg Hg/kg, while 1998 sediment concentrations in Sardis, Enid and Grenada Lakes were 0.112, 0.088 and 0.133 mg Hg/kg, respectively. Sediment mercury concentrations in 1999 were similar in all three lakes but, generally lower than 1998. Mean total mercury concentrations in edible fillets of fish collected from Enid Lake in 1998 were above the human health FDA action level (> 1.0 mg Hg/kg) for bass (1.40), crappie (1.69) and gar (1.89); however, tissue concentrations were less than 1.0 mg Hg/kg in carp (0.63) and catfish (0.82). Human hazard indexes for each species was > or = 1 for both adults and children, indicating that there is a potential for toxic effects to occur. In addition, calculated consumption limits indicate that adults may consume 4-12 oz. of fish per month, depending on the species consumed. For children, 2 oz. per month may be consumed. Further studies are needed to determine the exact environmental consequences and human health impacts associated with mercury contamination in North Mississippi and the Southeastern United States.

Toxicokinetic interactions and survival of Hyalella azteca exposed to binary mixtures of chlorpyrifos, dieldrin, and methyl mercury.

Chemical mixture interactions of chlorpyrifos, dieldrin, and methyl mercury were evaluated in Hyalella azteca. Survival of adult and juvenile organisms was evaluated following exposure to individual chemicals and in binary combinations. Binary interactions of the model chemicals on survival of adult and juvenile H. azteca were evaluated by concentration-response curve analysis as additive, synergistic, antagonistic, or independent. Chlorpyrifos and methyl mercury interacted additively, while dieldrin interacted independently with both chlorpyrifos and methyl mercury. Toxicodynamic interactions were evaluated by measuring accumulation and elimination of each model toxicant in the presence of a second toxicant. Chlorpyrifos significantly increased the amount of methyl mercury accumulated in the first 12 h of exposure. Dieldrin did not interact with chlorpyrifos or methyl mercury in the accumulation or elimination experiments. Accumulation of chlorpyrifos was not observed. Results of the current investigation demonstrate that chlorpyrifos and methyl mercury interact additively, which would otherwise be predicted to act independently.

Interactions of chlorpyrifos and methyl mercury: a mechanistic approach to assess chemical mixtures.

The mechanism of interaction between chlorpyrifos, an organophosphate insecticide, and methyl mercury was assessed utilizing the amphipod, Hyalella azteca. Previous studies have demonstrated that chlorpyrifos and methyl mercury interact additively with survival as the endpoint. In addition, exposure to chlorpyrifos and methyl mercury increased the accumulation and decreased the elimination of methyl mercury. To further examine the mechanism responsible for these interactions, the in vivo and in vitro inhibition of acetylcholinesterase enzyme activity was assessed following exposure to methyl mercury and chlorpyrifos. In vivo, methyl mercury antagonized the effects of chlorpyrifos on acetylcholinesterase inhibition. Additional studies demonstrated that methyl mercury did not affect the in vitro bioactivation of chlorpyrifos or the subsequent inhibition of acetylcholinesterase enzyme activity. Chemical-chemical interactions were examined utilizing chromatographic techniques and suggested the formation of a chlorpyrifos-methyl mercury complex. The formation of this complex may result in increased accumulation of methyl mercury, apparent additive toxicity, and protection against chlorpyrifos-mediated acetylcholinesterase inhibition.

Toxicological interactions of chlorpyrifos and methyl mercury in the amphipod, Hyalella azteca.

The mechanism of interaction between chlorpyrifos, an organophosphate insecticide, and methyl mercury, an organometal, was assessed utilizing the amphipod, Hyalella azteca. Previous studies have demonstrated that chlorpyrifos and methyl mercury interact additively, with survival as the endpoint. In addition, exposure to chlorpyrifos and methyl mercury increased the accumulation and decreased the elimination of methyl mercury. To elucidate the mechanism responsible for these interactions, biochemical mechanisms indicative of chlorpyrifos and methyl mercury toxicity were assessed in H. azteca. Biochemical endpoints that were evaluated include the inhibition of acetylcholinesterase enzyme and indicators of oxidative stress such as glutathione-S-transferase activity, lipid peroxidation, protein oxidation, and glutathione content. Methyl mercury antagonized the effects of chlorpyrifos in vivo on acetylcholinesterase inhibition. Methyl mercury did not induce oxidative damage; however, chlorpyrifos decreased glutathione-S-transferase activity. Additional studies demonstrated that methyl mercury did not affect the in vitro bioactivation of chlorpyrifos or the subsequent inhibition of acetylcholinesterase enzyme activity. Chemical-chemical interactions were examined utilizing chromatographic techniques. Results of thin layer chromatography suggested the formation of a chlorpyrifos-methyl mercury complex. The formation of this complex may result in increased accumulation of methyl mercury, apparent additive toxicity, and protection against chlorpyrifos mediated acetylcholinesterase inhibition.

Toxicological evaluation of constructed wetland habitat sediments utilizing Hyalella azteca 10-day sediment toxicity test and bacterial bioluminescence.

A toxicological evaluation was conducted on wetland habitats created as a result of run-off from agricultural areas. These temporary wetlands were created by using drop pipes as a means of reducing erosional cutting in agricultural fields. Toxicity bioassays utilizing bacterial bioluminescence and Hyalella azteca were used to assess sediment pore water and whole sediment, respectively. Inhibition of bacterial bioluminescence was initially used to determine relative toxicities of pore water from ten wetland sites. Constructed wetland sites were compared to the University of Mississippi Biological Field Station, a relatively pristine reference site. The H. azteca ten day sediment toxicity test was utilized to assess sediment from four selected sites using survival and growth as toxicological endpoints. Results from the toxicological evaluation, along with extensive ecological evaluations, were used to assess the best approach for implementation of temporary wetland habitats with existing agricultural practices.

Effect of arsenite, arsenate, and the herbicide monosodium methyl arsonate (MSMA) on hepatic metallothionein expression and lipid peroxidation in channel catfish.

Arsenic exerts its toxicity by the generation of reactive oxygen intermediates which caused lipid peroxidation and cellular damage. Metallothioneins (MTs) have been shown to be induced by oxidative stress and act as scavengers of reactive oxygen intermediates. Thus, hepatic MT was examined in channel catfish treated with the herbicide monosodium methyl arsonate (MSMA) and compared to equal doses of trivalent and pentavalent arsenic. Fish were exposed to 0.01, 0.1, and 1.0 mg/L of each compound for 1 week by static renewal. Hepatic MT was measured by the cadmium/hemoglobin (Cd/Hb) saturation assay, ELISA using antibodies raised against the first 10 amino acids of piscine MT, and Northern blot analysis using a cDNA encoding winter flounder hepatic MT. Cd/Hb and ELISA measurements of low molecular weight fractions from the hepatic cytosolic component of fish exposed to MSMA revealed a dose dependent increase in MT. MTs and MT mRNA of fish receiving the 1.0 mg/L dose were significantly induced vs control. Responses to arsenate exposure were more variable, but showed a trend toward a dose-dependent induction of MT and MT mRNA. MT mRNA and protein also showed a dose-dependent increase with arsenite exposure with no significant differences with untreated animals. Hepatic lipid peroxidation (as determined by TBARS) and glutathione was unaltered by any of the arsenical treatments. Thus, the lack of correlation between oxidative stress and MT expression suggest MT may not be a reliable indicator of oxidative stress. In addition, the induction of hepatic MT by various forms of As does not appear to be mediated through an oxidative stress mechanism in the liver.