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1.
Sci Total Environ ; 884: 163725, 2023 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-37116809

RESUMO

This study investigated critical metal (CM) geochemistry including rare earth elements (REEs), Co, Ni, and Mn in groundwaters below and surrounding two dredged material placement facilities (DMPFs). Metal concentrations are elevated at both sites, spanning several orders of magnitude. The highest CM concentrations measured exceed many environments considered as aqueous resources (Co and Ni > 1 mg L-1, REEs > 3 mg L-1). Correlations between sulfur and iron, major cations, and CMs indicate that oxidation of sulfides present in the DM releases metals both directly from sulfide minerals and indirectly through acid dissolution of and/or desorption from additional minerals. REE fractionation patterns indicate that their mobility in the groundwaters may be influenced by interactions with silicate, carbonate, and phosphate minerals. Significant positive Gd and Eu anomalies were observed, which may be attributed to increased mobility of Eu2+ and anthropogenic Gd. Nanogeochemical analysis of filtered samples revealed several REE-bearing nanoparticulate (diameter < 100 nm) species, some of which co-occurred with aluminum, suggesting an (oxy)hydroxide or a clay mineral component. Further characterization of soluble and nano scale geochemical speciation is needed to fully assess the viability of CM recovery from DM-associated groundwater. CM recovery from DM-associated waters can provide a beneficial use, both offsetting costs associated with disposal, and supplementing domestic CM resources.


Assuntos
Água Subterrânea , Metais Terras Raras , Monitoramento Ambiental , Metais/análise , Metais Terras Raras/análise , Água Subterrânea/química , Minerais/análise
2.
Toxics ; 10(5)2022 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-35622624

RESUMO

(1) Background: Disperse Blue 14, Disperse Red 9, Solvent Red 169 and Solvent Yellow 33 have been used to color smoke; however, they have not been comprehensively assessed for their potential health hazards. (2) Methods: To assess the effects of these dyes, zebrafish embryos were exposed from 6 to 120 h post fertilization (hpf) to 10-55 µM Disperse Red 9, 1-50 µM Solvent Red 169, 7.5-13.5 µM Solvent Yellow 33 or 133-314 µM Disperse Blue 14. Embryos were monitored for adverse effects on gene expression at 48 hpf as well as for mortality, development and behavior at 120 hpf. The dyes were examined for their potential to cross the blood-brain barrier. (3) Results: Solvent Yellow 33 and Disperse Blue 14 impaired development and behavior at all concentrations. Disperse Red 9 impaired behavior at all concentrations and development at all concentrations except for 10 µM. Solvent Red 169 caused no effects. Mortality was only seen in Disperse Blue 14 at 261.5 and 314 µM. Gene expression indicated impacts on neurodevelopment and folate and retinol metabolism as potential mechanisms of toxicity. (4) Conclusions: Smoke dyes have a high potential for causing developmental changes and neurotoxicity and should be examined more closely using comprehensive approaches as used here.

3.
Environ Toxicol Chem ; 41(5): 1260-1275, 2022 05.
Artigo em Inglês | MEDLINE | ID: mdl-35349191

RESUMO

Standard bioaccumulation tests are commonly conducted using Macoma nasuta (clam), and Alitta virens (polychaete) for marine tests, and Lumbriculus variegatus (an oligochaete) for freshwater tests. Because the interlaboratory variability associated with these tests is unknown, four experienced laboratories conducted standard 28-day bioaccumulation tests with the above species using sediments contaminated with polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). Chemical analysis of tissue samples was performed by a single laboratory. The intralaboratory variance among replicates was relatively low for PCB tissue concentrations, with coefficients of variation (CVs) ranging from 9% to 28% for all laboratories and species, with the exception of one laboratory reporting higher variability for L. variegatus (CV = 51%). Intralaboratory variance for PCB tissue concentrations was higher than interlaboratory variance for A. virens and L. variegatus, and the magnitude of difference (MOD) for laboratory means ranged from 1.4 to 2.0 across species. Intralaboratory variability was also low for lipid content, and lipid normalization of PCB and PAH body residues generally had little impact on variability. In addition to variability across bioassay laboratories, analytical variability was evaluated by different laboratories measuring the concentration of PCBs and total lipids in a subsample of tissue homogenate of sediment-exposed test organisms. Variability associated with tissue analysis was higher than bioassay laboratory variability only in tests with L. variegatus. Statistical differences between samples may be observed due to the low intralaboratory variability; however, the biological significance of these differences may be limited because the MOD is low. Considering the MOD when comparing bioaccumulation across treatments accounts for uncertainty related to inherent variability of the test in the interpretation of statistically significant results. Environ Toxicol Chem 2022;41:1260-1275. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. This article has been contributed to by US Government employees and their work is in the public domain in the USA.


Assuntos
Bivalves , Oligoquetos , Bifenilos Policlorados , Poluentes Químicos da Água , Animais , Bioacumulação , Sedimentos Geológicos/química , Lipídeos/análise , Bifenilos Policlorados/análise , Poluentes Químicos da Água/análise
4.
Toxics ; 9(1)2021 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-33435144

RESUMO

Solvent Violet 47 (SV47) and Disperse Blue 14 (DB14) are two anthraquinone dyes that were previously used in different formulations for the production of violet-colored smoke. Both dyes have shown potential for toxicity; however, there is no comprehensive understanding of their effects. Zebrafish embryos were exposed to SV47 or DB14 from 6 to 120 h post fertilization (hpf) to assess the dyes' potential adverse effects on developing embryos. The potential ability of both dyes to cross the blood-brain barrier was also assessed. At concentrations between 0.55 and 5.23 mg/L, SV47 showed a dose-dependent increase in mortality, jaw malformation, axis curvature, and edemas. At concentrations between 0.15 and 7.54 mg/L, DB14 did not have this same dose-dependence but had similar morphological outcomes at the highest doses. Nevertheless, while SV47 showed significant mortality from 4.20 mg/L, there was no significant mortality on embryos exposed to DB14. Regardless, decreased locomotor movement was observed at all concentrations of DB14, suggesting an adverse neurodevelopmental effect. Overall, our results showed that at similar concentrations, SV47 and DB14 caused different types of phenotypic effects in zebrafish embryos.

5.
Chemosphere ; 265: 129110, 2021 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-33272677

RESUMO

The deposition of metals into the environment as a result of military training activities remains a long-term concern for Defense organizations across the globe. Of particular concern for deposition and potential mobilization are antimony (Sb), arsenic (As), copper (Cu), lead (Pb), and tungsten (W), which are the focus of this review article. The fate, transport, and mobilization of these metals are complicated and depend on a variety of environmental factors that are often convoluted, heterogeneous, and site-dependent. While there have been many studies investigating contaminant mobilization on military training lands there exists a lack of cohesiveness surrounding the current state of knowledge for these five metals. The focus of this review article is to compile the current knowledge of the fate, transport, and ultimate risks presented by metals associated with different military training activities particularly as a result of small arms training activities, artillery/mortar ranges, battleruns, rocket ranges, and grenade courts. From there, we discuss emerging research results and finish with suggestions of where future research efforts and training range designs could be focused toward further reducing the deposition, limiting the migration, and decreasing risks presented by metals in the environment. Additionally, information presented here may offer insights into Sb, As, Cu, Pb, and W in other environmental settings.


Assuntos
Metais Pesados , Militares , Poluentes do Solo , Antimônio/análise , Meio Ambiente , Monitoramento Ambiental , Humanos , Metais Pesados/análise , Poluentes do Solo/análise
6.
Sci Total Environ ; 743: 140845, 2020 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-32758854

RESUMO

Detection of metal nanoparticles (NPs) in the environment is an analytical challenge of interest due to increasing use of nanomaterials in consumer and industrial products. Detecting NPs associated with human activities is affected by both the magnitude and variation in background concentrations of natural NPs. In this work, we investigated the potential release of titanium dioxide (TiO2) NPs from sunscreen in three recreational rivers, with a time-intensive sampling regime on one river, in order to determine the range and variability of natural, background titania (Ti). Conventional ICP analysis for total metal concentrations, single particle ICP-MS for NP concentrations, and electron microscopy aided in assessing mineralogical morphology and composition. Oxybenzone, a widely-used organic sunscreen, was measured and used as a surrogate for the intensity of recreational activity in the water. Statistically significant increases in Ti concentrations were observed in Clear Creek, CO during one recreation period, but the significance of other instances of recreation-associated Ti increases was unclear, in part due to storm impacts on the natural suspended sediment load of the stream. A comparison of three recreational rivers showed increases in both Ti mass concentrations and NP sizes occur during recreation in both Clear Creek, CO and the Salt River, AZ, but no detectable changes in the Truckee River, NV. However, size distributions were variable in background samples, which make the significance of differences observed during recreation unclear. These results underline that the release of engineered nanoparticles to a natural system cannot be detected without a well-defined background, including measures of its variability during the study period.


Assuntos
Nanopartículas Metálicas , Nanopartículas , Poluentes Químicos da Água/análise , Humanos , Rios , Protetores Solares/análise , Titânio/análise
7.
Talanta ; 217: 121008, 2020 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-32498881

RESUMO

Currently, no standard method exists for analyzing insensitive munition (IM) compounds in environmental matrices, with or without concurrent legacy munition compounds, resulting in potentially inaccurate determinations. The primary objective of this work was to develop new methods of extraction, pre-concentration, and analytical separation/quantitation of 17 legacy munition compounds along with several additional IM compounds, IM breakdown products, and other munition compounds that are not currently included in U. S. Environmental Protection Agency (EPA) Method 8330B. The eight additional compounds included were nitroguanidine, 3-nitro-1,2,4-triazol-5-one, picric acid, 2,4-dinitroanisole, 2,4-dinitrophenol, 2-nitrophenol, 4-nitrophenol, and new surrogate ortho-nitrobenzoic acid (o-NBA). Analytical methods were developed to enable sensitive, simultaneous detection and quantitation of the 24 IM and legacy compounds, including two orthogonal high-performance liquid chromatography (HPLC) column separations with either ultraviolet (UV) or mass spectrometric (MS) detection. Procedures were developed for simultaneous extraction of all 24 analytes and two surrogates (1,2-dinitrobenzene, 1,2-DNB; o-NBA) from high- and low-level aqueous matrices and solid matrices, using acidification, solid phase extraction (SPE), or solvent extraction (SE), respectively. For low-level aqueous samples extracted by SPE, all compounds were recovered within current Department of Defense Quality Systems Manual (DoD QSM) Ver5.3 accepted limits for aqueous samples analyzed by EPA Method 8330B (57-135%), except NQ, which was consistently recovered at approximately 50%. Likewise, all compounds were recovered from six geographically/geochemically unique soil types within current QSM accepted limits for solid samples analyzed by EPA Method 8330B (64-135%). Further, the majority of compounds were recovered from four tissue types within current limits for solids, with generally low recovery only for Tetryl (from 4 to 62%). A preparatory chromatographic interference removal procedure was adapted for tissue extracts, as various analytical interferences were observed for all studied tissue types.

8.
Bull Environ Contam Toxicol ; 104(4): 455-463, 2020 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-32108243

RESUMO

Carbon nanotubes (CNTs) have unique properties which can be modified through surface functionalization. The ability of several functionalized and un-functionalized CNTs to bind copper was investigated as a first step toward developing a printable CNT-based sensor to detect copper in aqueous systems. Binding capacity and specificity were shown to vary by functionalization and vendor. CNTs from two vendors were tested, and the equilibrium binding data was fitted using two isotherm models. Calculated qmax (mg/g) values indicated one vendor's carboxyl-functionalized CNTs had the greatest binding capacity (94-115 mg/g), while other carboxyl-functionalized CNTs and amine-functionalized CNTs had similar capacities to un-functionalized CNTs (15-30 mg/g). Hydroxyl-functionalized CNTs had the lowest copper binding capacity (7-8 mg/g) of the CNTs tested. Freundlich isotherms showed no obvious trends in binding affinity, but suggested that binding was primarily due to chemisorption. Variations in CNT size, functionalization percentage, and purity could explain, partially, the observed adsorption differences.


Assuntos
Cobre/análise , Nanotubos de Carbono/química , Poluentes Químicos da Água/análise , Adsorção , Propriedades de Superfície , Termodinâmica , Purificação da Água
9.
Chemosphere ; 240: 124958, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31726587

RESUMO

Degradation of insensitive munitions (IMs) by ultraviolet (UV) light has become a topic of concern following observations that some UV-degradation products have increased toxicity relative to parent compounds in aquatic organisms. The present investigation focused on the Army's IM formulation, IMX-101, which is composed of three IM constituents: 2,4-dinitroanisole (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), and nitroguanidine (NQ). The IM constituents and IMX-101 were irradiated in a UV photo-reactor and then administered to Daphnia pulex in acute (48 h) exposures comparing toxicities relative to the parent materials. UV-degradation of DNAN had little effect on mortality whereas mortality for UV-degraded NTO and NQ (and associated degradation products) increased by factors of 40.3 and 1240, respectively, making UV-degraded NQ the principle driver of toxicity when IMX-101 is UV-degraded. Toxicity investigations for specific products formed during UV-degradation of NQ, confirmed greater toxicity than the parent NQ for degradation products including guanidine, nitrite, ammonia, nitrosoguanidine, and cyanide. Summation of the individual toxic units for the complete set of individually measured UV-degradation products identified for NQ only accounted for 25% of the overall toxicity measured in the exposures to the UV-degraded NQ product mixture. From these toxic unit calculations, nitrite followed by CN- were the principal degradation products contributing to toxicity. Given the underestimation of toxicity using the sum toxic units for the individually measured UV-degradation products of NQ, we conclude that: (1) other unidentified NQ degradation products contributed principally to toxicity and/or (2) synergistic toxicological interactions occurred among the NQ degradation product mixture that exacerbated toxicity.


Assuntos
Anisóis/química , Guanidinas/efeitos da radiação , Triazóis/química , Raios Ultravioleta , Animais , Anisóis/toxicidade , Daphnia/efeitos dos fármacos , Poluentes Ambientais/química , Poluentes Ambientais/toxicidade , Guanidinas/toxicidade , Mutação , Nitrocompostos/química , Nitrocompostos/toxicidade , Testes de Toxicidade , Triazóis/toxicidade
10.
Environ Toxicol Chem ; 38(6): 1221-1230, 2019 06.
Artigo em Inglês | MEDLINE | ID: mdl-30790342

RESUMO

There are limited acute toxicity test methods for native North American marine species that are considered zooplankton for their entire life cycle. Examples of standardized marine zooplankton methods include mussel, bivalve, and echinoderm development tests that use a relatively short-lived planktonic larval stage, chronic life-cycle toxicity tests using epibenthic copepods, and a 24-h Acartia tonsa copepod test method. The objectives of the present study were to: 1) develop and evaluate a novel, 48-h acute toxicity test method using the marine North American copepod Pseudodiaptomus pelagicus that is planktonic for its entire life cycle, and 2) determine the sensitivity of P. pelagicus relative to commonly tested marine toxicity test species. The average (±1 standard deviation) median lethal concentrations (LC50s) for copper (Cu), phenanthrene, and un-ionized ammonia were 32 ± 15 µg/L, 161 ± 51 µg/L, and 1.08 ± 0.30 mg NH3 /L, respectively. These results placed P. pelagicus on the more sensitive end of Cu and phenanthrene species sensitivity distributions. The copepod was less sensitive to un-ionized ammonia than commonly tested marine species. This finding suggests that the acute P. pelagicus test method will allow a focus on assessing the impacts of persistent contaminants of concern with less confounding impact from naturally occurring ammonia released to the water from sources such as suspended sediments. Environ Toxicol Chem 2019;38:1221-1230. Published 2019 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.


Assuntos
Amônia/toxicidade , Organismos Aquáticos/efeitos dos fármacos , Copépodes/efeitos dos fármacos , Cobre/toxicidade , Fenantrenos/toxicidade , Animais , Bioensaio , Especificidade da Espécie , Testes de Toxicidade Aguda , Testes de Toxicidade Crônica , Poluentes Químicos da Água/toxicidade
11.
Environ Toxicol Chem ; 2018 Feb 23.
Artigo em Inglês | MEDLINE | ID: mdl-29473669

RESUMO

The synthesis of carbon-based nanomaterials is often inefficient, generating large amounts of soot with metals as waste by-product. Currently, there are no specific regulations for disposal of engineered nanomaterials or the waste by-products resulting from their synthesis, so it is presumed that by-products are disposed of in the same way as the parent (bulk) materials. We studied the terrestrial toxicity of soot from gadolinium metallofullerene nanomanufacturing on earthworms (Eisenia fetida) and isopods (Porcellio scaber). The metallofullerene soot consisted of carbon particle agglomerates in the nanometer and submicrometer ranges (1-100 and 101-999 nm, respectively), with metals used during nanomanufacturing detectable on the particles. Despite high metal concentrations (>100 000 mg/kg) in the soot, only a relatively small amount of metals leached out of a spiked field soil, suggesting only moderate mobility. Seven- and 14-d exposures in field soil demonstrated that the soot was only toxic to earthworms at high concentrations (>10 000 mg/kg); however, earthworms avoided spiked soils at lower concentrations (as low as 500 mg/kg) and at lower soil pH. The presence of soot in food and soil did not cause isopod avoidance. These data demonstrate that metallofullerene soot from nanomanufacturing may only be toxic to earthworms at high concentrations representative of improper disposal or accidental spills. However, our results indicate that terrestrial invertebrates may avoid soils contaminated with soot at sublethal concentrations. Environ Toxicol Chem 2018;9999:1-12. Published 2018 Wiley Periodicals, Inc. on behalf of SETAC. This article is a US government work, and as such, is in the public domain in the United States of America.

12.
Nanotoxicology ; 11(9-10): 1127-1139, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-29192531

RESUMO

As integration of nanoparticles (NPs) into products becomes more common, the need to address the paucity of chronic hazard information for aquatic environments required to determine risk potential increases. This study generated acute and chronic toxicity reference values for Ceriodaphnia dubia exposed to 20 and 100 nm silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs) to generate and evaluate potential differences in acute-to-chronic ratios (ACR) using two different feeding methods. A modified feeding procedure was employed alongside the standard procedures to investigate the influence of food on organism exposure. An 8-h period before food was added allowed direct organism exposure to NP dispersions (and associated ions) without food-to-NP interactions. The AgNPs [chronic lethal median concentrations (LC50) between 18.7 and 31.9 µg/L] were substantially more toxic than AuNPs (LC50 = 21 507 to >26 384 µg/L). The modified chronic testing method resulted in greater sensitivity in AgNPs exposures. However, the modified feeding ration had less of an effect in exposures to the larger (100 nm) AgNPs compared to smaller particles (20 nm). The ACRs for AgNPs using the standard feeding ration were 1.6 and 3.5 for 20 nm and 100 nm, respectively. The ACRs for AgNPs using the modified feeding ration were 3.4 and 7.6 for 20 nm and 100 nm NPs, respectively. This supports that the addition of the standard feeding ration decreases C. dubia chronic sensitivity to AgNPs, although it must also be recognized organisms may be sensitized due to less access to food. The ACRs for 20 nm and 100 nm AuNPs (standard ration only) were 4.0 and 3.0, respectively. It is important to also consider that dissolved Ag+ ions are more toxic than AgNPs, based on both acute toxicity values in the cited literature and chronic toxicity thresholds generated in this study that support existing thresholds that Ag+ are likely protective of AgNPs effects.


Assuntos
Daphnia/efeitos dos fármacos , Ouro/toxicidade , Nanopartículas Metálicas/toxicidade , Prata/toxicidade , Poluentes Químicos da Água/toxicidade , Animais , Ouro/química , Dose Letal Mediana , Nanopartículas Metálicas/química , Tamanho da Partícula , Prata/química , Propriedades de Superfície , Testes de Toxicidade Aguda , Testes de Toxicidade Crônica , Poluentes Químicos da Água/química
13.
Environ Sci Technol ; 51(23): 13755-13762, 2017 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-29053267

RESUMO

This investigation builds on previous studies on military-relevant tungsten (W) to more thoroughly explore environmental pathways and bioaccumulation kinetics during direct soil exposure versus trophic transfer and elucidate its relative accumulation and speciation in different snail organs. The modeled steady-state concentration and bioaccumulation factor (BAF) of W from soil into cabbage were 302 mg/kg and 0.55, respectively. Steady-state concentrations (34 mg/kg) and BAF values (0.05) obtained for the snail directly exposed to contaminated soil were lower than trophic transfer by consumption of W-contaminated cabbage (tissue concentration of 86 mg/kg; BAF of 0.36). Thus, consumption of contaminated food is the most important pathway for W mobility in this food chain. The highest concentrations of W compartmentalization were in the snail's hepatopancreas based on wet chemistry and synchrotron-based investigations. Chemical speciation via inductively couple plasma mass spectrometry showed a higher degree of polytungstate partitioning in the hepatopancreas relative to the rest of the body. Based on synchrotron analysis, W was incorporated into the shell matrix during exposure, particularly during the regeneration of damaged shell. This offers the potential for application of the shell as a longer-term biomonitoring and forensics tool for historic exposure.


Assuntos
Brassica , Cadeia Alimentar , Tungstênio/farmacocinética , Animais , Monitoramento Ambiental , Cinética , Modelos Animais
14.
Nanotoxicology ; 11(4): 546-557, 2017 May.
Artigo em Inglês | MEDLINE | ID: mdl-28463032

RESUMO

The unique behavior of engineered nanomaterials (ENM) in aqueous media and dynamic changes in particle settling, agglomeration and dissolution rates is a challenge to the consistency, reliability and interpretation of standard aquatic hazard bioassay results. While the toxicological endpoints (e.g., survival, growth, reproduction, etc.) in ecotoxicity bioassays are largely applicable to ENMs, the standard methods as written for dissolved substances are confounded by the dynamic settling, agglomeration and dissolution of particulate ENMs during the bioassay. A testing framework was designed to serve as a starting point to identify approaches for the consistent conduct of aquatic hazard tests that account for the behavior of ENMs in test media and suitable data collection to support representative exposure metrology. The framework was demonstrated by conducting three case studies testing ENMs with functionally distinct characteristics and behaviors. Pretests with a temporal sampling of particle concentration, agglomeration and dissolution were conducted on each ENM in test media. Results indicated that a silver nanoparticle (AgNP) powder was not dispersible, a nano-TiO2 powder was dispersible but unstable, and a polyvinylpyrrolidinone-coated AgNP was relatively stable in test media. Based on these functional results, Ceriodaphnia dubia bioassays were conducted to compare different exposure summary methods (nominal, arithmetic average, geometric average, time-weighted average) for calculating and expressing toxicity endpoints. Results indicated that while arithmetic means were effective for expressing the toxicity of more stable materials, time-weighted averaged concentrations were appropriate for the unstable nano-TiO2.


Assuntos
Daphnia/efeitos dos fármacos , Ecotoxicologia/métodos , Nanopartículas/toxicidade , Prata/toxicidade , Titânio/toxicidade , Poluentes Químicos da Água/toxicidade , Animais , Bioensaio , Reprodutibilidade dos Testes , Solubilidade , Testes de Toxicidade/métodos
15.
Chemosphere ; 176: 125-130, 2017 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-28260653

RESUMO

Natural organic matter (NOM) can have a significant influence on the mobility and fate of inorganic oxyanions, such as arsenic and selenium, in the environment. There is evidence to suggest that interactions between NOM and these oxyanions are facilitated by bridging cations (primarily Fe3+) through the formation of ternary complexes. Building on previous work characterizing ternary complexes formed in the laboratory using purified NOM, this study describes the extraction and characterization of intact ternary complexes directly from a soil matrix. The complexes are stable to the basic extraction conditions (pH 12) and do not appear to change when the pH of the extract is adjusted back to neutral. The results suggest that ternary complexes between NOM, cations, and inorganic oxyanions exist in natural soils and could play a role in the speciation of inorganic oxyanions in environmental matrices.


Assuntos
Complexos de Coordenação/isolamento & purificação , Solo/química , Ânions/química , Arsênio/química , Arsênio/isolamento & purificação , Cátions/química , Complexos de Coordenação/análise , Meio Ambiente , Substâncias Húmicas , Concentração de Íons de Hidrogênio , Substâncias Macromoleculares/química , Substâncias Macromoleculares/isolamento & purificação , Compostos Orgânicos/química , Selênio/química , Selênio/isolamento & purificação
16.
Environ Toxicol Chem ; 36(8): 2050-2057, 2017 08.
Artigo em Inglês | MEDLINE | ID: mdl-28059482

RESUMO

Insensitive munitions are desirable alternatives to historically used formulations, such as 2,4,6-trinitrotoluene (TNT), because of their so-called insensitivity to unintended detonation. The insensitive munition IMX-101 is a mixture of 2,4-dinitroanisole (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), and nitroguanidine (NQ). Environmental releases of munitions may be from production wastewaters or training; these munitions may be exposed to ultraviolet (UV) light. Therefore, it is useful to understand the relative toxicity of IMX-101 and its constituents both before and after photodegradation. The intent of the present study was to generate relative hazard information by exposing the standard ecotoxicological model Ceriodaphnia dubia to each insensitive munition constituent individually and to IMX-101 before and after the exposure solution was irradiated in a UV photoreactor. Without photodegradation, DNAN was more toxic (median lethal concentration [LC50] = 43 mg/L) than the other 2 constituents and it contributed predominantly to the toxicity of IMX-101 (LC50 = 206 mg/L) based on toxic units. Toxicity was observed only at high levels of NQ (LC50 = 1174 mg/L) and pH-adjusted NTO (LC50 = 799 mg/L). The toxicity of IMX-101 is lower than literature-reported TNT toxicity. Photodegradation efficiency was greater at lower insensitive munition concentrations. The observed degradation was greatest for NQ (42-99%), which in turn corresponded to the greatest relative increase in toxicity (100-1000-fold). Modest percent of degradation (4-18%) and increases in phototoxicity (2-100-fold) were observed for NTO and DNAN. Photodegraded NQ products were the predominant source of toxicity of photodegraded IMX-101. Future work involves research to enable analytical and computational confirmation of the specific degradation compounds inducing the observed photoenhanced toxicity. Environ Toxicol Chem 2017;36:2050-2057. Published 2017 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.


Assuntos
Anisóis/toxicidade , Substâncias Explosivas/toxicidade , Guanidinas/toxicidade , Nitrocompostos/toxicidade , Fotólise , Triazóis/toxicidade , Poluentes Químicos da Água/toxicidade , Animais , Anisóis/efeitos da radiação , Cladocera/efeitos dos fármacos , Monitoramento Ambiental , Substâncias Explosivas/efeitos da radiação , Guanidinas/efeitos da radiação , Dose Letal Mediana , Nitrocompostos/efeitos da radiação , Triazóis/efeitos da radiação , Trinitrotolueno/toxicidade , Estados Unidos , Poluentes Químicos da Água/efeitos da radiação
17.
Chemosphere ; 166: 192-196, 2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27697707

RESUMO

The mobility and fate of inorganic oxyanions in the environment can be greatly influenced by interactions with natural organic matter (NOM). There is increasing evidence that this interaction between two anionic species is facilitated by cationic bridges, but detailed mechanistic studies into this system are challenging due to the heterogeneous nature of NOM. This work examines the ability of cations (FeIII, CrIII, AlIII, or GaIII) to form ternary complexes with Suwannee River humic acid (SRHA) and the oxyanions of As (AsIII and AsV) and Se (SeIV and SeVI). Complexes were characterized by separating SRHA from unbound species using size exclusion chromatography coupled to ICP-MS to determine its metal content. Unlike CrIII and FeIII, the post-transition metal ions AlIII and GaIII proved ineffective at forming ternary complexes with any of the oxyanions, although minor complexation was observed with GaIII, suggesting that electrostatic interactions are not the primary driving force behind the stabilization of these ternary complexes. The results also show differences in the behavior of FeIII and CrIII that may indicate that the two cations stabilize the ternary complexes by different mechanisms.


Assuntos
Substâncias Húmicas , Oxigênio/química , Metais Pesados/química , Rios/química
18.
Chemosphere ; 162: 222-7, 2016 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-27497530

RESUMO

Engineered nanomaterials (ENMs) are being incorporated into a variety of consumer products due to unique properties that offer a variety of advantages over bulk materials. Understanding of the nano-specific risk associated with nano-enabled technologies, however, continues to lag behind research and development, registration with regulators, and commercialization. One example of a nano-enabled technology is nanosilver ink, which can be used in commercial ink-jet printers for the development of low-cost printable electronics. This investigation utilizes a tiered EHS framework to evaluate the potential nano-specific release, exposure and hazard associated with typical use of both nanosilver ink and printed circuits. The framework guides determination of the potential for ENM release from both forms of the technology in simulated use scenarios, including spilling of the ink, aqueous release (washing) from the circuits and UV light exposure. The as-supplied ink merits nano-specific consideration based on the presence of nanoparticles and their persistence in environmentally-relevant media. The material released from the printed circuits upon aqueous exposure was characterized by a number of analysis techniques, including ultracentrifugation and single particle ICP-MS, and the results suggest that a vast majority of the material was ionic in nature and nano-specific regulatory scrutiny may be less relevant.


Assuntos
Condutividade Elétrica , Tinta , Nanopartículas Metálicas , Nanotecnologia , Prata/química , Impressão , Medição de Risco
19.
Bull Environ Contam Toxicol ; 96(6): 714-9, 2016 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-27016940

RESUMO

Yuma Proving Grounds (YPG) in western Arizona is a testing range where Depleted uranium (DU) penetrators have been historically fired. A portion of the fired DU penetrators are being managed under controlled conditions by leaving them in place. The widespread use of DU in armor-penetrating weapons has raised environmental and human health concerns. The present study is focused on the onsite management approach and on the potential interactions with plants local to YPG. A 30 day study was conducted to assess the toxicity of DU corrosion products (e.g., schoepite and meta-schoepite) in two grass species that are native to YPG, Bermuda (Cynodon dactylon) and Purple Threeawn (Aristida purpurea). In addition, the ability for plants to uptake DU was studied. The results of this study show a much lower threshold for biomass toxicity and higher plant concentrations, particularly in the roots than shoots, compared to previous studies.


Assuntos
Cynodon/efeitos dos fármacos , Plantas/efeitos dos fármacos , Urânio/toxicidade , Arizona , Biomassa , Urânio/análise , Armas
20.
Bull Environ Contam Toxicol ; 96(6): 773-8, 2016 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-26988223

RESUMO

Real-time detection of hydrocarbon contaminants in the environment presents analytical challenges because traditional laboratory-based techniques are cumbersome and not readily field portable. In the current work, a method for rapid and semi-quantitative detection of organic contaminants, primarily crude oil, in natural water and soil matrices has been developed. Detection limits in the parts per million and parts per billion were accomplished when using visual and digital detection methods, respectively. The extraction technique was modified from standard methodologies used for hydrocarbon analysis and provides a straight-forward separation technique that can remove interference from complex natural constituents. For water samples this method is semi-quantitative, with recoveries ranging from 70 % to 130 %, while measurements of soil samples are more qualitative due to lower extraction efficiencies related to the limitations of field-deployable procedures.


Assuntos
Fluorescência , Poluentes do Solo/análise , Solo/química , Poluentes da Água/análise , Água/química , Hidrocarbonetos/análise , Petróleo/análise
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