Particle Morphology and Elemental Analysis of Lung Tissue from Post-9/11 Military Personnel with Biopsy-Proven Lung Disease.

The relationship between exposure to inhaled inorganic particulate matter and risk for deployment-related lung disease in military personnel is unclear due in part to difficulties characterizing individual exposure to airborne hazards. We evaluated the association between self-reported deployment exposures and particulate matter (PM) contained in lung tissue from previously deployed personnel with lung disease ("deployers"). The PM in deployer tissues was compared to normal lung tissue PM using the analytical results of scanning electron microscopy and inductively coupled plasma mass spectrometry. The majority of PM phases for both the deployers and the controls were sub-micrometer in size and were compositionally classified as aluminum and zirconium oxides, carbonaceous particles, iron oxides, titanium oxides, silica, other silicates, and other metals. The proportion of silica and other silicates was significantly higher in the retained dust from military veterans with biopsy-confirmed deployment-related lung disease compared to the control subjects. Within the deployer population, those who had combat jobs had a higher total PM burden, though the difference was not statistically significant. These findings have important implications for understanding the role of inhaled inorganic dusts in the risk for lung injury in previously deployed military veterans.

Seasonal changes of trace elements, nutrients, dissolved organic matter, and coastal acidification over the largest oyster reef in the Western Mississippi Sound, USA.

Seasonal changes of trace elements, nutrients, dissolved organic matter (DOM), and carbonate system parameters were evaluated over the largest deteriorating oyster reef in the Western Mississippi Sound using data collected during spring, summer, and winter of 2018, and summer of 2019. Higher concentrations of Pb (224%), Cu (211%), Zn (2400%), and Ca (240%) were observed during winter of 2018 compared to summer 2019. Phosphate and ammonia concentrations were higher (> 800%) during both summers of 2018 and 2019 than winter of 2018. Among the three distinct DOM components identified, two terrestrial humic-like components were more abundant during both spring (12% and 36%) and summer (11% and 33%) of 2018 than winter of 2018, implying a relatively lesser supply of humic-like components from terrestrial sources during winter. On the other hand, the protein-like component was more abundant during summer of 2019 compared to rest of the study period, suggesting a higher rate of autochthonous production during summer 2019. In addition, to their significant depth-wise variation, ocean acidification parameters including pH, pCO2, CO32-, and carbonate saturation states were all higher during both summers of 2018 and 2019. The measured variables such as trace elements, organic carbon, suspended particulates, and acidification parameters exhibited conservative mixing behavior against salinity. These observations have strong implications for the health of the oyster reefs, which provides ecologically important habitats and supports the economy of the Gulf Coast.

Removal of CrO42-, a Nonradioactive Surrogate of 99TcO4-, Using LDH-Mo3S13 Nanosheets.

Removal of chromate (CrO42-) and pertechnetate (TcO4-) from the Hanford Low Activity Waste (LAW) is beneficial as it impacts the cost, life cycle, operational complexity of the Waste Treatment and Immobilization Plant (WTP), and integrity of vitrified glass for nuclear waste disposal. Here, we report the application of [MoIV3S13]2- intercalated layer double hydroxides (LDH-Mo3S13) for the removal of CrO42- as a surrogate for TcO4-, from ppm to ppb levels from water and a simulated LAW off-gas condensate of Hanford's WTP. LDH-Mo3S13 removes CrO42- from the LAW condensate stream, having a pH of 7.5, from ppm (∼9.086 × 104 ppb of Cr6+) to below 1 ppb levels with distribution constant (Kd) values of up to ∼107 mL/g. Analysis of postadsorbed solids indicates that CrO42- removal mainly proceeds by reduction of Cr6+ to Cr3+. This study sets the first example of a metal sulfide intercalated LDH for the removal of CrO42-, as relevant to TcO4-, from the simulated off-gas condensate streams of Hanford's LAW melter which contains highly concentrated competitive anions, namely F-, Cl-, CO32-, NO3-, BO33-, NO2-, SO42-, and B4O72-. LDH-Mo3S13's remarkable removal efficiency makes it a promising sorbent to remediate CrO42-/TcO4- from surface water and an off-gas condensate of nuclear waste.

Evaluating hydrogeochemical characteristics of groundwater and surface water in the Upper Pearl River Watershed, USA.

The groundwater quality of the Upper Pearl River Watershed (UPRW) and surface water quality of the basin's outlet, Ross Barnett Reservoir (RBR), are critically important because of growing demands for drinking, agriculture, and industrial use in the region. To identify factors affecting water quality and characterize the surface water outlet and the watershed's groundwater, geochemical and statistical analyses were performed using results from various hydrogeochemical parameters. Based on surface geology, groundwater samples analyzed (n = 51) within the watershed were partitioned into three recharge zones: North, Mid, and South. Precipitation and rock-water interactions were identified to dominantly influence the groundwater chemistry in the region. The chemistry of the surface water samples (n = 9), on the other hand, was influenced more by precipitation with minor contribution from the proximal aquifer system. Principal component analysis (PCA) revealed that two groundwater recharge zones and RBR samples exhibited significant clustering. The groundwater had a complex array of parameters influencing its chemistry owing to diverse properties, including Na, Ca, Mg, alkalinity, and conductivity. Comparing land use at the sub-watershed level with the water quality parameters showed that agriculture and development could have contributed nitrate, especially to the groundwater in the south zone. However, a general lack of distinct relationship between land use and water quality, along with detection of excess nitrate in select wells suggested that the water in the region was likely affected by point sources, such as poultry farms. The research recommends evaluating point sources of pollution to cater to future water management in the region.

Pollution assessment and land use land cover influence on trace metal distribution in sediments from five aquatic systems in southern USA.

Trace elements and heavy metals concentrate in aquatic sediments, potentially endangering benthic organisms. Comparing the concentration of metals in different aquatic bodies will help evaluate their accumulation and distribution characteristics within these systems. Metal pollution and enrichment indices in sediments from diverse aquatic systems in Southern USA, including agricultural ponds, man-made reservoir, river, swamp, and coastal environment were investigated. Following total digestion of the sediments, the concentrations of chromium (Cr), cobalt (Co), copper (Cu), zinc (Zn), arsenic (As), selenium (Se), cadmium (Cd), antimony (Sb), lead (Pb), and uranium (U) were measured using inductively coupled plasma-mass spectrometry (ICP-MS). Pb was found to be highly enriched in the sediment samples from all five environments. The samples from coastal and agricultural ponds showed highest degree of anthropogenic modification (enrichment factor >10), especially with Se, U, and Pb. Agricultural ponds, previously unknown as a metal hotspot, had the most deteriorated sediment quality as determined by high pollution load index (>1) and contamination factor (>6) for Cd and U. Principal component analysis comparing land use land cover distribution surrounding the aquatic systems to metal concentrations confirmed that agriculture-related land activities correlated well with majority of the metals. Overall, compared to agricultural ponds and coastal regions, sediments in river, swamp and man-made reservoir systems contained relatively fewer metal pollutants, the former two serving as collection points for metal-laden fertilizers and chemicals. The research provides key insights into simultaneously comparing metal accumulation in multiple water bodies and is useful to test and develop effective sediment quality guidelines.

An Evaluation Research About Effects of Characterized Cadmium Selenide (CdSe) and Lead Selenide (PbSe) Quantum Dots on Brine Shrimp (Artemia salina).

Quantum dots (QDs), such as cadmium selenide (CdSe) and lead selenide (PbSe) exhibit excellent optical, magnetic and chemical properties due to their extremely size (ca. 1-10 nm) and are attractive semiconductor nanomaterials for optical studies and energy storage. In this study, aqueous synthesis of CdSe and PbSe QDs in a size range of 2-10 nm was described. Synthesized QDs were characterized using SEM and TEM, DLS, zeta potential, FTIR, EDX and XRD. Highest accumulation (72.5 ± 5.8 mg L-1) of PbSe QDs occurred at 10 ppm suspensions. In general accumulation increased up to 48 h exposure then fluctuate tended to decline. For CdSe QDs, accumulation tended to decrease for 72 h exposure except that for 5 ppm groups. For the elimination period, in general, the elimination levels of PbSe and CdSe QDs from exposed individuals decreased (p < 0.05) even it has some fluctuate.

Assessment of impact of α-Fe2 O3 and γ-Fe2 O3 nanoparticles on phytoplankton species Selenastrum capricornutum and Nannochloropsis oculata.

In this study, the impact of alpha-iron oxide (α-Fe2 O3 , 20-40 nm) and gamma iron oxide (γ-Fe2 O3 , 20-40 nm) nanoparticles (NPs) on phytoplankton species Selenastrum capricornutum and Nannochloropsis oculata was investigated Characterizations of the NPs were systematically carried out by TEM, dynamic light scattering, zeta potential, X-ray diffraction, SEM, and Fourier transformation infrared spectroscopy. Acute toxicity was tested between 0.2 and 50 mg/L for each NP for a period of 72 hours exposure. γ-Fe2 O3 NP inhibited development of N oculata at the rate of 54% in 0.2 mg/L group with a high mortality rate of up to 82%. α-Fe2 O3 NPs were less toxic that induced 97% mortality on N oculata at 10 mg/L suspensions. In contrast, α-Fe2 O3 NP inhibited growth of S capricornutum strongly (73%) in 0.2 mg/L group. γ-Fe2 O3 NPs showed similar growth inhibition (72%) on S capricornutum in 10 mg/L suspensions. Despite the differential effects, the results indicated acute toxicity of α-Fe2 O3 and γ-Fe2 O3 NPs on N oculata and S capricornutum.

Assessment of Oxidative Stress on Artemia salina and Daphnia magna After Exposure to Zn and ZnO Nanoparticles.

In this study, the effect of zinc nanoparticles (Zn NPs) and zinc oxide nanoparticles (ZnO NPs) on Artemia salina and Daphnia magna, the primary consumer organisms were investigated. In this sense, investigation of trophic transfer and ecological sustainability potentials among living things, such as fish and crustaceans that are at the top of the food chain were also aimed. Zn NPs in the size of 40-60 nm and 80-100 nm and ZnO NPs (10-30 nm) were administered to A. salina and D. manga (respectively in total 105000 and 14000 individuals) in seven groups (Control, 0.2, 1, 5, 10, 25 ve 50 ppm) with three repetitions for a period of 72 h. Intensive and possible misuse of nanoscale materials is one of the biggest threats to the environment and all living things worldwide. Therefore, the control mechanisms for the use of NPs need to be established.

Phytotoxic effect of silver nanoparticles on seed germination and growth of terrestrial plants.

Silver nanoparticles (AgNP) exhibit size and concentration dependent toxicity to terrestrial plants, especially crops. AgNP exposure could decrease seed germination, inhibit seedling growth, affect mass and length of roots and shoots. The phytotoxic pathway has been partly understood. Silver (as element, ion or AgNP) accumulates in roots/leaves and triggers the defense mechanism at cellular and tissue levels, which alters metabolism, antioxidant activities and related proteomic expression. Botanical changes (either increase or decrease) in response to AgNP exposure include reactive oxygen species generation, superoxide dismutase activities, H2O2 level, total chlorophyll, proline, carotenoid, ascorbate and glutathione contents, etc. Such processes lead to abnormal morphological changes, suppression of photosynthesis and/or transpiration, and other symptoms. Although neutral or beneficial effects are also reported depending on plant species, adverse effects dominate in majority of the studies. More in depth research is needed to confidently draw any conclusions and to guide legislation and regulations.

CALCIUM OXIDE REMEDIATION OF ANTHROPOGENIC CONTAMINATION OF WATER AT THE GBNERR IN MISSISSIPPI.

Grand Bay National Estuarine Research Reserve (GBNERR) is an important ecosystem in the Mississippi Gulf Coast. The GBNERR may be a potential source for contamination with anthropogenic bacterial pathogens that may play a significant role in the causation of waterborne human diseases. The objective of this study was to evaluate the interaction of physicochemical and microbiological water quality parameters at the GBNERR, determine quantitative levels and establish the potential for remediation of post-contamination of water and seafood by human fecal pollution from anthropogenic sources at the reserve. Water samples were collected aseptically from Bayous Heron, Cumbest, Point Aux Chenes Bay and Bangs Lake (Pine-O-Pine). Physicochemical parameters were determined using standard protocols. Eight bacteria/parasitic species including Cryptosporidium were concentrated from water samples by membrane filtration. Water samples were tested for the presence of traditional indicator microorganisms including: heterotrophic (HPC), total coliforms (TC), fecal coliforms (FC) and enterococcus (ENT) in CFU/ml concentrations. Mean values of temperature, specific conductivity, dissolved oxygen and pH were within acceptable levels in comparison to MDEQ, USEPA and the USGS standards during the time of investigation. However, the values of turbidity in Grand Bay water exceeded USEPA recommended levels in several occasions during the investigation. Data from this study indicates significant variability (p < 0.0001) in mean bacteria concentrations between sites. The data also indicates significant impact of Calcium oxide treatment in the remediation of post contamination and survival of pathogens from the GBNERR Bayous Heron, Cumbest and Pine-O-Pine when compared with control findings. The interaction of physicochemical and microbiological parameters of water through external chemical manipulation by Calcium oxide may provide utility in the remediation of post-contamination with anthropogenic pathogens such as E. coli, Enterococci, Campylobacter, Vibrio, Giardia and Cryptosporidium. Presence of high numbers of indicator bacteria suggest public health concerns for oyster and shellfish consumers as well as other water contact activities. Hence, control strategies should be developed and implemented to prevent or remediate any future contamination of the GBNERR waters citing the economic impact of such contamination on shell fish fishing activities on the reserve.

SODIUM BICARBONATE REMEDIATION OF ANTHROPOGENIC CONTAMINATION OF WATER AT THE GBNERR IN MISSISSIPPI.

Grand Bay National Estuarine Research Reserve (GBNERR) is an important ecosystem in the Mississippi Gulf Coast. The GBNERR may be a potential source for contamination with anthropogenic bacterial pathogens that may play a significant role in the causation of waterborne human diseases. The objective of this study was to evaluate the interaction of physicochemical and microbiological water quality parameters at the GBNERR, determine quantitative levels and establish the potential for remediation of post-contamination of water and seafood by human fecal pollution from anthropogenic sources at the reserve. Water samples were collected aseptically from Bayous Heron, Cumbest, Point Aux Chenes Bay and Bangs Lake (Pine-O-Pine). Physicochemical parameters were determined using standard protocols. Eight bacterial species including Campylobacter were concentrated from water samples by membrane filtration. Water samples were tested for the presence of traditional indicator microorganisms including: heterotrophic (HPC), total coliforms (TC), fecal coliforms (FC) and enterococcus (ENT) in CFU/ml concentrations. Mean values of temperature, specific conductivity, dissolved oxygen and pH were within acceptable levels in comparison to MDEQ, USEPA and the USGS standards during the time of investigation. However, the values of turbidity in Grand Bay water exceeded USEPA recommended levels in several occasions during the investigation. Data from this study indicates significant variability (p < 0.0001) in mean bacteria concentrations between sites. The data also indicates significant impact of Sodium bicarbonate treatment in the remediation of post contamination and survival of pathogens from the GBNERR Bayous Heron, Cumbest and Pine-O-Pine when compared with control findings. The interaction of physicochemical and microbiological parameters of water through external chemical manipulation by Sodium bicarbonate may provide utility in the remediation of post-contamination with anthropogenic pathogens such as E. coli, Enterococci, Campylobacter, Vibrio, Giardia and Cryptosporidium. Presence of high numbers of indicator bacteria suggest public health concerns for oyster and shellfish consumers as well as other water contact activities. Hence, control strategies should be developed and implemented to prevent or remediate any future contamination of the GBNERR waters citing the economic impact of such contamination on shell fish fishing activities at the reserve.

Kinetics and Thermodynamics of Uranium (VI) Adsorption onto Humic Acid Derived from Leonardite.

Humic acid (HA) is well known as an inexpensive and effective adsorbent for heavy metal ions. However, the thermodynamics of uranium (U) adsorption onto HA is not fully understood. This study aimed to understand the kinetics and isotherms of U(VI) adsorption onto HA under different temperatures from acidic water. A leonardite-derived HA was characterized for its ash content, elemental compositions, and acidic functional groups, and used for the removal of U (VI) from acidic aqueous solutions via batch experiments at initial concentrations of 0-100 mg·L-1 at 298, 308 and 318 K. ICP-MS was used to determine the U(VI) concentrations in solutions before and after reacting with the HA. The rate and capacity of HA adsorbing U(VI) increased with the temperature. Adsorption kinetic data was best fitted to the pseudo second-order model. This, together with FTIR spectra, indicated a chemisorption of U(VI) by HA. Equilibrium adsorption data was best fitted to the Langmuir and Temkin models. Thermodynamic parameters such as equilibrium constant (K0), standard Gibbs free energy (ΔG0), standard enthalpy change (ΔH0), and standard entropy change (ΔS0), indicated that U(VI) adsorption onto HA was endothermic and spontaneous. The co-existence of cations (Cu2+, Co2+, Cd2+ and Pb2+) and anions (HPO42- and SO42-) reduced U(VI) adsorption. The high propensity and capacity of leonardite-derived HA adsorbing U(VI) suggests that it has the potential for cost-effective removal of U(VI) from acidic contaminated waters.

Simultaneous separation of arsenic and cadmium from interfering salt matrix of multivitamin/mineral supplements by sequential coprecipitation and determination by inductively coupled plasma mass spectrometry.

Multivitamin/mineral (MVM) supplements possess highly saline matrix which, unless eliminated, precludes accurate determination of trace amounts of toxic metal impurities by inductively coupled plasma mass spectrometry (ICP-MS). Multi-step separations (up to four-steps) are described in literature; often for single element determinations due to difficulties in removing the matrix components. In this study, we developed a three-step sequential coprecipitation procedure for simultaneous separation of As and Cd impurities from MVM supplements for determination by ICP-MS. The procedure provided effective elimination of salt matrix, including Ca, Mg and KCl along with the interfering molybdenum (Mo) and tin (Sn) from MVM solutions. KCl, Mo and Sn were removed by two-step Mg(OH)2 coprecipitation to about 34 µg mL-1 K (ca. 31 µg mL-1 Cl) and 0.4 µg mL-1 Mo. Levels of Sn and Na were not significant. A third coprecipitation of the resulting MVM solution with HF + NH4OH mixture precipitated virtually all Ca and Mg to as low as 1 and 10 µg mL-1, respectively. The recoveries for As and Cd in the spiked MVM solutions were about 96% and 95%, respectively. The accuracy of the method was validated with analysis of multivitamin/multielement tablets certified reference material (SRM 3280). Experimental values were 112 ± 37 ng g-1 for 75As, and 76 ± 5, 79 ± 5, and 78 ± 7 ng g-1 for 110Cd, 111Cd and 114Cd isotopes, respectively, that were not significantly different from the certified values of As (132 ± 44 ng g-1) and Cd (80.2 ± 0.9 ng g-1) at 95% confidence level. Several commercially available MVM supplements were analyzed with the procedure. Mean As levels measured in the tablets varied between 24 and 128 ng g-1 and that for Cd were between 28 and 125 ng g-1 indicating total amount of As or Cd ingested per serving size were below the safe daily exposure limits. In addition, the results obtained for As and Cd with the procedure were lower in comparison to the values reported in literature indicating that ICP-MS analysis of complex MVM supplements could be prone to higher risks of inaccuracy without removal of interfering matrix.

Electrokinetic-enhanced phytoremediation of uranium-contaminated soil using sunflower and Indian mustard.

Electrokinetic-enhanced phytoremediation is an effective technology to decontaminate heavy metal contaminated soil. In this study, we examined the effects of electrokinetic treatments on plant uptake and bioaccumulation of U from soils with various U sources. Redistribution of uranium in soils as affected by planting and electrokinetic treatments was investigated. The soil was spiked with 100 mg kg-1 UO2, UO3, and UO2(NO3)2. After sunflower and Indian mustard grew for 60 days, 1 voltage of direct-current was applied across the soils for 9 days. The results indicated that U uptake in both plants were significantly enhanced by electrokinetic treatments from soil with UO3 and UO2(NO3)2. U was more accumulated in roots than in shoots. Electrokinetic treatments were effective on lowering soil pH near the anode region. Overall, uranium (U) removal efficiency reached 3.4-4.3% from soils with UO3 and uranyl with both plants while that from soil with UO2 was 0.7-0.8%. Electrokinetic remediation treatment significantly enhanced the U removal efficiency (5-6%) from soils with UO3 and uranyl but it was 0.8-1.3% from soil with UO2, indicating significant effects of U species and electrokinetic enhancement on U bioaccumulation. This study implies the potential feasibility of electrokinetic-enhanced phytoremediation of U soils with sunflower and Indian mustard.

Laboratory spiking process of soil with various uranium and other heavy metals.

Laboratory studies using metal spiked soils are challenging due to soil heterogeneity. This work provides an easy, quick, precise, and accurate technique for the preparation of spiked soils for laboratory research. The process described spiking soil with various uranium species and other heavy metals for laboratory scale pilot experiments under various biogeochemical conditions. The procedure involves grinding both dry soil and metal chemicals into the fine powder. The spiked soil mixture was further homogenized through a modified splitting and combining of the sample by diagonal flipping using plastic sheeting. Comparison of measured concentrations with theoretical values were obtained with <20% precision and accuracy. However, tradition spiking method with metal solution often yielded high heterogeneous spiked soils due to strong metal adsorption in soils. Re-drying and re-grinding of soils were required following the spiking in order to homogenize treated soils, generating inhalable particulates. Thus appropriate personal protective equipment and practices are required for the safety concern. The present method with metal salt powder proved a safe, useful, quick, accurate and precise, and homogenized soil spiking method. •ability to prepare spiked soil with multiple elements•prepared soil at any level of loading•the spiked soil was homogenous for controlled studies.

Toxicity of As in Crassostrea virginica (Gmelin, 1791) from the Northern Gulf of Mexico at the presence of Zn and its antioxidant defense mechanisms.

Reactive oxygen species (ROS) such as the free radicals (e.g. hydroxyl, nitric acid, superoxide) cause damage to lipids, proteins and DNA. Increased production of ROS occurs from pollution. Process of removal or neutralization of ROS is achieved through antioxidants enzyme defense systems and provide homeostasis within biological systems. Aerobic organisms have complex antioxidant systems using enzymatic and non-enzymatic antioxidants to prevent overproduction of ROS. This study examined the toxic effects of arsenic and zinc on Eastern oysters, their interaction and resulting enzymatic responses. Cellular damage as indicated with lipid peroxidation and antioxidant defensive enzyme activities (superoxide dismutase, SOD; glutathione peroxidase, GPX and catalase, CAT) were measured in the hepatopancreas of Eastern oysters exposed to single and combined treatments of arsenic and zinc for 30 days. The results showed either arsenic or zinc exposure significantly increased the lipid peroxidation and triggered antioxidant defenses. Activities of antioxidant enzymes (SOD, GPX and CAT) were markedly elevated upon expose of As or Zn. However, at the presence of Zn, As toxicity expressed as lipid oxidation significantly decreased as well as accordingly decreased activities of antioxidant enzymes. This revealed that the presence of Zn showed a significantly antagonistic effect on arsenic toxicity in Eastern oysters from Northern Gulf of Mexico.

Removal of inorganic mercury by selective extraction and coprecipitation for determination of methylmercury in mercury-contaminated soils by chemical vapor generation inductively coupled plasma mass spectrometry (CVG-ICP-MS).

A procedure is developed for selective extraction of methylmercury (CH3Hg+) from heavily Hg-contaminated soils and sediments for determination by chemical vapor generation inductively coupled plasma mass spectrometry (CVG-ICP-MS). Soils artificially contaminated with 40 µg g-1 inorganic mercury (Hg2+) or methylmercury chloride (CH3HgCl) were agitated by shaking or exposing to ultrasounds in dilute hydrochloric acid (HCl) or nitric acid (HNO3) solutions at room temperature. Extractions in HCl (5 or 10% v/v) resulted in substantial leaching of Hg2+ from soils, whereas 5% (v/v) HNO3 provided selectivity for quantitative extraction of CH3Hg+ with minimum Hg2+ leaching. Agitation with ultrasounds in 5% (v/v) HNO3 for about 3 min was sufficient for extraction of all CH3Hg+ from soils. Coprecipitations with Fe(OH)3, Bi(OH)3 and HgS were investigated for removal of residual Hg2+ in soil extracts. Hydroxide precipitations were not effective. Thiourea or l-cysteine added to soil extracts prior to hydroxide precipitation improved precipitation of Hg2+, but also resulted in removal of CH3Hg+. HgS precipitation was made with dilute ammonium sulfide solution, (NH4)2S. Adding 30 µL of 0.35 mol L-1 (NH4)2S to soil extracts in 5% (v/v) HNO3 resulted in removal of all residual Hg2+ without impacting CH3Hg+ levels. Vapor generation was carried out by reacting Hg2+-free soil extracts with 1% (m/v) NaBH4. No significant interferences were observed from (NH4)2S on the vapor generation from CH3Hg+. The slopes of the calibration curves for CH3HgCl standard solutions in 5% (v/v) HNO3 with and without (NH4)2S were similar. Limits of detection (LOD, 3s method) were around 0.08 µg L-1 for 5% (v/v) HNO3 blanks (n = 10) and 0.10 µg L-1 for 5% (v/v) HNO3 + 0.005 mol L-1 (NH4)2S blanks (n = 10). Percent relative standard deviation (%RSD) for five replicate measurements varied between 3.1% and 6.4% at 1.0 CH3HgCl level. The method is validated by analysis of two certified reference materials (CRM); purely Methylmercury sediment (SQC1238, 10.00 ±â€¯0.291 ng g-1 CH3Hg+) and Hg-contaminated Estuarine sediment (ERM - CC580, 75 ±â€¯4 ng g-1 CH3Hg+ and 132 ±â€¯3 µg g-1 total Hg). CH3Hg+ values for SQC1238 were between 13.0 and 13.2 ng g-1, and 79 and 81 ng g-1 for ERM - CC580. Hg-contaminated soils (57-96 µg g-1 total Hg) collected from the floodplains of Oak Ridge, TN were analyzed for CH3Hg+ using the procedure by CVG-ICPMS. CH3Hg+ levels ranged from 30 to 51 ng g-1 and did not correlate with total Hg levels (R2 = 0.01).

Sequential coprecipitation and matrix removal for determination of cadmium impurities from multivitamin supplements by inductively coupled plasma mass spectrometry and method validation by isotope dilution analysis of SRM 3280 multivitamin/multielement tablets.

In this paper, we examined three different sequential coprecipitation schemes based on Mg(OH)2 and CaF2 precipitation using triethylamine (TEA) and hydrofluoric acid (HF), respectively, for determination of cadmium (Cd) impurities from multivitamin/mineral (MVM) supplements by isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS). The schemes involved three-step coprecipitation with either TEA alone or in combination with HF and are designated as Scheme 1 (TEA-TEA-TEA), Scheme 2 (TEA-HF-TEA) and Scheme 3 (HF-TEA-TEA) according to the addition sequence of each reagent. Experiments were carried out with MVM solutions spiked with 60 µg L-1 Cd from a multielement standard solution. All schemes provided quantitative separation of Cd from MVM matrix. Scheme 1 was the least effective in removal of interfering concomitant elements, molybdenum (Mo) and tin (Sn). Scheme 2 performed better for Sn, but failed in eliminating Mo. Scheme 3 was the most effective in eliminating both Mo and Sn. Mo levels in test MVM solutions reduced from 4.3 µg mL-1 to as low as 0.014 µg mL-1 while that for Sn decreased from 0.5 µg mL-1 to 0.018 µg mL-1 allowing interference-free determination of Cd to be achieved. Salt-matrix due to Mg, Ca, P and K along with the essential elements (Mn, Fe, Cu and Zn) levels was also reduced significantly. Reagent blanks from HF and TEA were insignificant (0.008 µg L-1) allowing a limit of detection of 0.004 µg L-1 or 0.26 ng g-1 Cd to be achieved (3σ, n = 6). The performance of the coprecipitation method (Scheme 3) was validated by determination of Cd in multivitamin/multielement tablets certified reference material (SRM 3280) by ID-ICP-MS. Experimental results (ng g-1) and recoveries were 78.8 ± 4.7 (98.5%), 77.9 ± 5.2 (97.4%) and 76.5 ± 4.8 (95.6%) for 110Cd, 111Cd and 114Cd isotopes, respectively. Several commercial MVM supplements were analyzed using the method. Mean Cd concentration ranged from 21.4 ng g-1 to 93.3 ng g-1. These values are much lower than those reported to date for various MVM supplements by ICP-MS determinations without chemical separation.

Triethylamine-assisted Mg(OH)2 coprecipitation/preconcentration for determination of trace metals and rare earth elements in seawater by inductively coupled plasma mass spectrometry (ICP-MS).

In this paper, we report an improved magnesium hydroxide, Mg(OH)2, coprecipitation method for the determination of 16 trace elements (Al, V, Cr, Mn, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Sb, Sn and Pb) and 18 rare earth elements (REEs), including Sc, Y, U and Th in seawater and estuarine water samples. The procedure involves coprecipitation of the trace elements and REEs on Mg(OH)2 upon addition of a small volume of triethylamine (TEA) followed by analysis of the dissolved pellet solutions by inductively coupled plasma mass spectrometry (ICP-MS). Three-step sequential coprecipitation was carried out on 10 mL aliquots of seawater to eliminate the matrix ions and to preconcentrate the analytes of interest into a 1 mL final volume. Spike recoveries varied from 85% (Th) to 105% (Y). Calcium (Ca), sodium (Na) and potassium (K) matrices were virtually eliminated from the analysis solutions. Collision reaction interface (CRI) technology utilizing H2 and He gases was employed to determine its effectiveness in removing the spectral interferences originating from the residual Mg matrix, TEA and plasma gases. H2 was more effective than He in reducing spectral interferences from TEA and plasma gases. Limits of detection (LODs) ranged from 0.01 ng L-1 (Ho) to 72 ng L-1 (Al). The method was validated by using certified seawater (CASS-4) and estuarine water (SLEW-3) reference materials. Precision for five (n = 5) replicate measurements were between 1.2% (Pr) and 18% (Lu). Fe, Pb, Sn, and Zn impurities in TEA were significant in comparison to the levels in CASS-4 and SLEW-3, while relatively high background signals impacted determinations of low levels of Sc and Th. The effects of these hurdles on precision and accuracy were alleviated by measuring these elements in spiked CASS-4 and SLEW-3.

ASSESSMENT OF ANIMAL MODELS AS SURROGATES FOR HUMAN TUMORS FROM THREE DIFFERENT ORGANS.

The compositional balance and distribution of trace metals/elements in various body tissues are essential key players in tissue and cellular homeostasis. Low Zn levels as well as overexpression of metalothioneins were implicated in the development and progression of various cancers including the prostate. Nonetheless, wider elemental profiles that relate cancer and normal phenotypes with regards to metal homeostasis were not well elucidated in the literature. Moreover, laboratory animals are currently used as accepted models for studying cancer but the level of their representation of actual cancer tissues was not clear. This study is attempting to assess the relevance of animal models currently in use, as surrogates for cancer and establish their relationship to actual normal and cancer tissues from humans. The major focus of this study was to investigate the differential relationship of metal concentrations and profiles in cancer and normal tissues from cadavers of humans and their comparison to established animal models representing organ cancers. The working hypothesis was that elemental/metal concentrations and profiles seen in post mortem will show significant differences between normal and cancer-derived tissues as well as between various tissue types in humans, rats, and dogs. This study also establishes critical elemental/metal profiles that may be relevant in providing correlations with the development of three major cancers. Normal human and tumor tissues of cadaverous lung, breast, and liver used in this study were obtained from US Biomax Company and relevant animal models (Sprague-dawley and Brown Norwegian rats as well as dogs; were obtained from Jackson Laboratories and the Mississippi State Veterinary Laboratory in Pearl, MS), to analyze for elements and test the hypothesis. Tissue samples were prepared using standardized digestion procedures necessary for use with the Inductively Coupled Plasma-Atomic Emission mass Spectrometry (ICP-MS) to determine the concentrations and profiles of 21 elements including Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Na, Ni, Pb, Sb, Se, Sr, Tl, V, and Zn. Our data supports the notion that metal/elemental homeostasis is essential for normal tissue function and that elemental variations in content, distributions, and ranking are tissue specific as well as carcinoma and species-specific. Analysis of data showed significant variations in elemental content and distribution profiles/ranking between animal models and actual human tissues consistent with the hypothesis. It is concluded that elemental homeostasis is essential for normal tissue function and that shifts in their distribution and content are essential in determining the use of animal models as surrogates for studying cancer. These results are promising and warrant further studies to confirm the relevance of animal models in relation to their use as pre-clinical tools for examining targeted cancer therapeutics.