Analysis of gunshot residues from nontoxic ammunition: a contribution to health and environmental analysis.

This study's aim was to determine the presence, as well as to evaluate the health and environmental impacts, of chemical elements from firearm shots during shooter practice at outdoor shooting ranges, both in the environment and on the shooters' hands. Two high-precision devices were used for measuring suspended particles that are released during discharge of Taurus PT 100 .40 caliber pistols. The analysis of collected data allowed the identification of specific distribution patterns of samples that were adsorbed. Moreover, samples were collected from the opisthenar area of the hand to investigate both the occurrence and deposition of particles and chemical elements through scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS). The results indicate that copper, lead, and zinc concentration profiles will be able to delimit and reveal more precise details regarding shots made with nontoxic ammunition (NTA). In particular, the residual graphic analysis indicated that the majority of metal deposited in the shooter's hand is zinc. Further, the metals barium and lead also were detected. Due to the exposure to these elements, it could be concluded that engineering controls and administrative management should be sought in order to avoid human overexposure and environmental release of these airborne toxic metals.

Insights from barium variability in a Siderastrea siderea coral in the northwestern Gulf of Mexico.

Coral Ba/Ca is a proxy for seawater barium concentration that varies with upwelling, terrigenous input, and marine productivity whereas coral Sr/Ca varies with temperature. We examine monthly coral Ba/Ca and Sr/Ca before and during offshore oil exploration in a Siderastrea siderea coral from West Flower Garden Bank located on the continental shelf edge in the Gulf of Mexico. Coral Ba/Ca variations lack pulses driven by upwelling or river outflow and are not in sync with coral Sr/Ca that exhibit a different seasonal pattern. Seasonal variations in chlorophyll-a concentration negatively correlate with coral Ba/Ca explaining 25% of that variability. A significant increase in mean coral Ba/Ca of 1.76 µmol/mol between 1931-1944 and 1976-2004 corresponds to the increase in the United States barite production and consumption primarily used in offshore oil drilling, which escalated in the 1970s, suggesting oil drilling operations are increasing seawater Ba concentration in the Gulf of Mexico.

Simultaneous determination of Ba, Co, Fe, and Ni in nuts by high-resolution continuum source atomic absorption spectrometry after extraction induced by solid-oil-water emulsion breaking.

This paper describes the simultaneous determination of Ba, Co, Fe, and Ni in nuts by high-resolution continuum source atomic absorption spectrometry after extraction induced by solid-oil-water emulsion breaking. Extraction yields ranged from 94.9 for Ba to 109.8% for Fe. Simultaneous measurements were carried out at secondary lines of Ba, Co, Fe, and Ni. The limits of detection and quantification were, respectively, 3.819 and 1.146 mg L-1 for Ba, 2.274 and 7.421 µg L-1 for Co, 0.095 and 0.285 mg L-1 for Fe, and 2.138 and 6.614 µg L-1 for Ni. The precision ranged from 3.1 to 4.2%, 1.5 to 8.0%, 1.6 to 6.6%, and 0.4 to 6.1% for Ba, Co, Fe and Ni, respectively. The method accuracy was assessed by recovery tests and comparison of the results obtained by the proposed extraction method with those obtained after acid digestion. Recoveries ranged from 93.5 for Ni to 104.5% for Co.

Detection of Pb, Ba, and Sb in Cadaveric Maggots and Pupae by ICP-MS.

The concentrations of lead (Pb), barium (Ba), and antimony (Sb), characteristic of GSR, were determined in soil sediments and immature (larvae) of cadaveric flies of the family Calliphoridae, by inductively coupled plasma mass spectrometry (ICP-MS). This research refers to a case study from two real crime scenes in which the corpses were in an advanced state of decomposition. In case 1, the victim had holes similar to gunshot wounds, and in case 2, there was no evidence of perforations in the corpse. Soil sediment collection was performed at three different points of the terrain, at a minimum distance of 10 m from the corpse, for cases 1 and 2. In relation to the collection of immatures, larvae were collected in regions of the mouth, nose, and orifices similar to the entry of firearms projectile into the body, for case 1, and collection of larvae and pupae, located on the body and underneath it, for case 2. It was possible to detect and quantify the three elements of interest (Pb, Ba, and Sb) by ICP-MS in both sediment and cadaveric larvae. Concentrations of 4.44, 8.74, and 0.08 µg/g were obtained for Pb, Ba, and Sb, respectively, in the soil for case 1. For the case 2, the concentrations in Pb, Ba, and Sb were from 16.34 to 26.02 µg/g; from 32.64 to 57.97 µg/g and from 0.042 to 0.30 µg/g, respectively. In the larvae, Pb, Ba, and Sb were quantified in cases 1 and 2 with a concentration of 6.28 and 1.78 µg/g for Pb, 1.49 and 2.94 µg/g for Ba, 0.50 µg/g and

Trace elements influence the hatching success and emergence of Caretta caretta and Chelonia mydas.

Trace elements from industrial, domestic and agricultural activities can be transferred into marine environments, affecting the survival of sea species. Due to their global distribution, sea turtles are recognized as indicators of ocean pollution. The aim of this work was to quantify Ba, Cd, Cr, Cu, Fe, Mn, Pb, Sr and Zn using inductively coupled plasma optical emission spectrometry (ICP-OES) in the eggs and offspring of Caretta caretta and Chelonia mydas from two important nesting beaches, Guanabara Beach, Anchieta, and Trindade/Martim Vaz Island, Espírito Santo, Brazil. C. mydas pups and eggs collected on Trindade/Martim Vaz Island presented significant differences in Ba, Cr, Cu, Mn and Sr (p < 0.001). Higher concentrations of Ba, Pb, and Sr were detected in eggs of this species in comparison to those of C. caretta on Guanabara Beach, Anchieta. Ba and Cd presented higher concentrations in pups than in eggs of C. caretta, which could indicate nesting pollution. Positive correlations between trace element concentrations and hatching success in C. caretta nests from Guanabara Beach, Anchieta, could be identified for Cu and Zn (r²â€¯= 0.86, F2.7 = 21, p < 0.001). Emergence success was influenced by Cu and Cd (r²â€¯= 0.84, F2.7 = 18.9, p = 0.002). In addition, Ba and Cd also influenced the emergence sucess (r²â€¯= 0.56, F2, 10 = 6.29, p = 0.017). The hatching success of C. mydas was influenced by the concentration of Cu (r²â€¯= 0.53, F2.14 = 7.82, p = 0.005). Further studies including the analyzed areas and migratory routes should be performed to promote conservation management at these beaches.

Spatial variability and solubility of barium in a petroleum well-drilling waste disposal area.

The petroleum industry generates a range of wastes which is often are disposed in soil close to the well location, negatively affecting soil and water quality. The objective of this study was to evaluate the solubility and map the spatial variability of barium in a potentially contaminated area. The study area consisted of a petroleum well-drilling waste disposal site located in the municipality of Mato Rico-PR. A large georeferenced sampling grid was organized. Soil samples were collected at depths of 30, 60, 90, and 120 cm for determination of the "pseudo-total" concentrations and geochemical fractionation of barium. The barium concentrations showed spatial dependence, which permitted the use of geostatistical interpolators. Regarding depth, the depth of 0-30 cm showed the largest contaminated area; however, higher concentrations of barium were found at the depth of 60-90 cm. The results of geochemical fractionation showed that the analyzed samples contained percentages higher than 99% in the non-labile fraction (residual). These results indicate clearly that the barium was in a condition of low solubility, even for samples that had the highest concentrations, presenting low-environmental risk.

Examining the utility of coral Ba/Ca as a proxy for river discharge and hydroclimate variability at Coiba Island, Gulf of Chirquí, Panamá.

Panamá's extreme hydroclimate seasonality is driven by Intertropical Convergence Zone rainfall and resulting runoff. River discharge (Q) carries terrestrially-derived barium to coastal waters that can be recorded in coral. We present a Ba/Ca record (1996-1917) generated from a Porites coral colony in the Gulf of Chiriquí near Coiba Island (Panamá) to understand regional hydroclimate. Here coral Ba/Ca is correlated to instrumental Q (R=0.67, p<0.001), producing a seasonally-resolved Reduced Major Axis regression of Ba/Ca (µmol/mol)=Q (m3/s)×0.006±0.001 (µmol/mol)(m3/s)-1+4.579±0.151. Our results support work in the neighboring Gulf of Panamá that determined seawater Ba/Ca, controlled by Q, is correlated to coral Ba/Ca (LaVigne et al., 2016). Additionally, the Coiba coral Ba/Ca records at least 5 El Niño events and identified 22 of the 37 wet seasons with below average precipitation. These data corroborate the Q proxy and provide insight into the use of coral Ba/Ca as an El Niño and drought indicator.

Determination of (226)Ra in produced water by liquid scintillation counting.

It is proposed a method for the determination of (226)Ra in offshore platform liquid effluent samples (produced water). The method is based on a two-phase liquid scintillation counting system and allows for the direct and simple determination of (226)Ra content. Samples with high barium content may also have high (226)Ra concentration. Therefore, the sample volume is based on the barium concentration and ranges from 10 mL to 100 mL. Our new method was tested using multiple real samples and was compared with the BaSO4 precipitation method. The results based on the LSC were 30% higher than the precipitation method, which is attributed to the self-absorption of alpha particles in the BaSO4 precipitate. The determination of both (226)Ra and (228)Ra in the liquid effluent of offshore oil platforms is mandatory in Brazil. Thus, a second method of accurately assessing (228)Ra content remains necessary.

Is otolith microchemistry (Sr: Ca and Ba:Ca ratios) useful to identify Mugil curema populations in the southeastern Caribbean Sea?

The aim of the present study was to evaluate the potential use of otolith microchemistry (Sr:Ca and Ba:Ca ratios) to identify silver mullet, Mugil curema, populations in Southeastern Caribbean Sea. Fish samples were collected in 7 areas of Nueva Esparta State (Venezuela). The otolith Sr:Ca and Ba:Ca ratios and water Sr:Ca were determined (by ICP-OES and EDTA volumetric method). Otoliths Sr:Ca and Ba:Ca ratios and Sr:Ca partition coefficient of mullets in Cubagua island (south of the State) were significantly different from ratios in La Guardia (north of the State). A discriminant analysis of otolith Sr:Ca and Ba:Ca ratios separated Cubagua Island from La Guardia values. These results suggest the existence of different mullet groups in the Southeastern Caribbean Sea. For this, the simultaneous use of Sr:Ca and Ba:Ca ratios could be a potential tool to identify populations in the study area.

Is otolith microchemistry (Sr: Ca and Ba:Ca ratios) useful to identify Mugil curema populations in the southeastern Caribbean Sea? / A microquímica do otólito é um indicador do habitat de Mugil curema no sudeste do Mar Caribenho?

The aim of the present study was to evaluate the potential use of otolith microchemistry (Sr:Ca and Ba:Ca ratios) to identify silver mullet, Mugil curema, populations in Southeastern Caribbean Sea. Fish samples were collected in 7 areas of Nueva Esparta State (Venezuela). The otolith Sr:Ca and Ba:Ca ratios and water Sr:Ca were determined (by ICP-OES and EDTA volumetric method). Otoliths Sr:Ca and Ba:Ca ratios and Sr:Ca partition coefficient of mullets in Cubagua island (south of the State) were significantly different from ratios in La Guardia (north of the State). A discriminant analysis of otolith Sr:Ca and Ba:Ca ratios separated Cubagua Island from La Guardia values. These results suggest the existence of different mullet groups in the Southeastern Caribbean Sea. For this, the simultaneous use of Sr:Ca and Ba:Ca ratios could be a potential tool to identify populations in the study area.(AU)

O objetivo do presente estudo foi avaliar o potencial uso da microquímica do otólito (razões Sr:Ca e Ba:Ca) para identificar distintas populações de tainha, Mugil curema, no sudeste do mar caribenho. Os peixes foram coletados em 7 áreas do estado de Nueva Esparta (Venezuela). As razões Sr:Ca e Ba:Ca do otólito e a razão Sr:Ca da água foram determinadas (pelo ICP-OES e EDTA método volumétrico). As razões de Sr:Ca e Ba:Ca dos otólitos e o coeficiente de partição das tainhas da Ilha Cubagua (sul do estado) foram significativamente diferentes das razões de La Guardia (norte do estado). A análise discriminante das razões de Sr:Ca e Ba:Ca dos otólitos separa os valores da Ilha Cubagua e de La Guardia. Estes resultados sugerem a existência de diferentes grupos de Mugil curema no sudeste do mar Caribenho e que o uso simultâneo das razões Sr:Ca e Ba:Ca poderiam ser uma potencial ferramenta para identificar as populações da área de estudo.(AU)

Is otolith microchemistry (Sr: Ca and Ba:Ca ratios) useful to identify Mugil curema populations in the southeastern Caribbean Sea? / A microquímica do otólito é um indicador do habitat de Mugil curema no sudeste do Mar Caribenho?

Abstract The aim of the present study was to evaluate the potential use of otolith microchemistry (Sr:Ca and Ba:Ca ratios) to identify silver mullet, Mugil curema, populations in Southeastern Caribbean Sea. Fish samples were collected in 7 areas of Nueva Esparta State (Venezuela). The otolith Sr:Ca and Ba:Ca ratios and water Sr:Ca were determined (by ICP-OES and EDTA volumetric method). Otoliths Sr:Ca and Ba:Ca ratios and Sr:Ca partition coefficient of mullets in Cubagua island (south of the State) were significantly different from ratios in La Guardia (north of the State). A discriminant analysis of otolith Sr:Ca and Ba:Ca ratios separated Cubagua Island from La Guardia values. These results suggest the existence of different mullet groups in the Southeastern Caribbean Sea. For this, the simultaneous use of Sr:Ca and Ba:Ca ratios could be a potential tool to identify populations in the study area.

Resumo O objetivo do presente estudo foi avaliar o potencial uso da microquímica do otólito (razões Sr:Ca e Ba:Ca) para identificar distintas populações de tainha, Mugil curema, no sudeste do mar caribenho. Os peixes foram coletados em 7 áreas do estado de Nueva Esparta (Venezuela). As razões Sr:Ca e Ba:Ca do otólito e a razão Sr:Ca da água foram determinadas (pelo ICP-OES e EDTA método volumétrico). As razões de Sr:Ca e Ba:Ca dos otólitos e o coeficiente de partição das tainhas da Ilha Cubagua (sul do estado) foram significativamente diferentes das razões de La Guardia (norte do estado). A análise discriminante das razões de Sr:Ca e Ba:Ca dos otólitos separa os valores da Ilha Cubagua e de La Guardia. Estes resultados sugerem a existência de diferentes grupos de Mugil curema no sudeste do mar Caribenho e que o uso simultâneo das razões Sr:Ca e Ba:Ca poderiam ser uma potencial ferramenta para identificar as populações da área de estudo.

An early-branching microbialite cyanobacterium forms intracellular carbonates.

Cyanobacteria have affected major geochemical cycles (carbon, nitrogen, and oxygen) on Earth for billions of years. In particular, they have played a major role in the formation of calcium carbonates (i.e., calcification), which has been considered to be an extracellular process. We identified a cyanobacterium in modern microbialites in Lake Alchichica (Mexico) that forms intracellular amorphous calcium-magnesium-strontium-barium carbonate inclusions about 270 nanometers in average diameter, revealing an unexplored pathway for calcification. Phylogenetic analyses place this cyanobacterium within the deeply divergent order Gloeobacterales. The chemical composition and structure of the intracellular precipitates suggest some level of cellular control on the biomineralization process. This discovery expands the diversity of organisms capable of forming amorphous calcium carbonates.

The Ba/Ca record of corals from the Southern Gulf of Mexico: contributions from land-use changes, fluvial discharge and oil-drilling muds.

The Ba/Ca in the growth bands of Montastraea faveolata from the Veracruz Reef System was used to reconstruct the long-term environmental change associated to anthropogenic activity in the Southern Gulf of Mexico (SGM). The 168-yr coral record shows two periods of distinct Ba concentrations: a pre-industrial period (1835-1965: 7.54 micromol/mol) followed by an industrial one (1966-2000: 8.57 micromol/mol). As human population quadrupoled during the latter, sediment load in the fluvial discharge also increased due to changes in land-use, yielding a 14% increase in the Ba-levels. A remarkable finding is that the periods at which the coral Ba/Ca ratio losses its correlation with fluvial discharge coincide exactly with peak periods of high barite consumption (used for oil drilling) in the Northern Gulf of Mexico, and the onset of oil drilling in the SGM. This finding suggests that barite may be one of the dominant sources for dissolved-Ba in the SGM.

Development of the concept of spatial-temporal mask for testing effects of discharge from well-drilling activities on biological communities.

This paper describes the use of Bayesian spatial models to develop the concept of a spatial-temporal mask for the purpose of identifying regions in which before and after drilling effects are most clearly defined and from which the consequences of exposure of macrofauna and meiofauna to the release of drilling discharges can be evaluated over time. To determine the effects of drilling fluids and drill-cuttings on the marine benthic community, it is essential to know not only where discharged materials ended up within the possible impact area, but also the chemical concentrations to which biota were exposed during and after drilling. Barium and light hydrocarbons were used as chemical tracers for water-based and non-aqueous-based fluids in a shallow water site in the Campos Basin, off the coast of Brazil. Since the site showed evidence of exposure to waste material from earlier drilling, the analysis needed to take into account the background concentrations of these compounds. Using the Bayesian models, concentrations at unsampled sites were predicted and regions altered and previously contaminated were identified.

Use of multitracers for the study of water mixing in the Paraíba do Sul River estuary.

Multitracers were used to study water mixing in the Paraíba do Sul River estuary region in August 2007 (dry season) and March 2008 (rainy season) and to evaluate the reach of the river plume in the direction of the open ocean. Two sampling campaigns were carried out, each in a different season. Based on these results, it was possible to conclude that the multitracers used in this study (salinity, Si, Ba and U, as well as the radium isotopes 223Ra, 224Ra, 226Ra and 228Ra) presented satisfactory results toward defining the plume reach and determining the residence time and water-mixing processes in the estuary. A strong correlation was observed between tracers and the distance to the coast. During the low river water discharge period, the riverine water took about 10 days to reach open ocean waters (salinity approximately 35). During the rainy period this value decreased to 6 days. Based on the radium results, it was possible to calculate diffusion coefficients (K(h)) of 23 km(2) d(-1) and 38 km(2) d(-1) for 224Ra and 223Ra, respectively, during the dry season (winter). Values of 65 km(2) d(-1) and 68 km(2) d(-1) for 223Ra and 224Ra, respectively, were found for the rainy period (summer).

Statistical mixture design development of digestion methods for Oyster tissue using inductively coupled plasma optical emission spectrometry for the determination of metallic ions.

The quantitative determination of chemical elements in organic or biological samples is an important analytical problem. Normally the elements to be determined in the organic matrix must be transformed into a simple inorganic form. A digestion method by heating on a block digestor has been developed for the determination of Al, As, Ba, Ca, Cd, Co, Cu, Fe, Mg, Mn, V and Zn in Oyster tissue by ICP OES. A simplex centroid statistical mixture design has been used to study the effects of changing HNO(3), HCl and H(2)O(2) reagent proportions on the digestion of these samples. Response surface and principal component analyses show that the species Ca, Cd, Cu, Fe, Mg, Mn and Zn have very similar analytical tendencies under this experiment. By means of mixture modeling maximum recoveries for these ions were predicted using 19%, 18% and 63% of the HCl, HNO(3) and H(2)O(2) pseudocomponent mixtures, respectively. This corresponds to 21.4%, 30.8% and 47.8% of the HCl, HNO(3) and H(2)O(2) commercial solutions. Furthermore the As, Co and V ions present large recoveries for these mixtures as well. The Al and Ba ion recoveries are seen to be independent of the mixture proportions. The analysis of Oyster tissue reference material (SRM 1566b - NIST) under optimized conditions at the selected wavelengths resulted in ion recoveries between 90% and 100%.

Optical density and chemical composition of microfilled and microhybrid composite resins.

This study evaluated the optical density of two microfilled and two microhybrid resins, as well as the composition of these materials with regard to their optical density. Cavities prepared in 12 2-mm- or 4-mm-thick acrylic plastic plates were filled with Z250 (3M-ESPE), A110 (3M-ESPE), Charisma (Heraeus-Kulzer) and DurafillVS (Heraeus-Kulzer). The resin increments (2-mm-thick) were light-cured for 40 s. Three 0.12-s radiographic exposures were made of each #2 acrylic plastic plate. DenOptix system optical plates were used to obtain the digital images. Three readings of the composite resin surface were made in each radiograph, totalizing 216 readings. The mean of highest and lowest grey-scale values was obtained. Two specimens of each composite resin were prepared for SEM analysis of the chemical elements related to optical density, using energy dispersive x-ray analysis (EDX). The results were subjected to Shapiro-Wilk's test, ANOVA, Tukey's test at 1% level of significance and Pearson's correlation. The mean grey-scale values at 2 mm and 4 mm were: Z250 = 154.27a and 185.33w; A110 = 46.77b and 63.05y; Charisma = 163.40c and 200.46z; DurafillVS = 43.92b and 58.99x, respectively. Pearson's test did not show any positive correlation between optical density and percentage weight of optical density chemical elements. It was concluded that the microhybrid resins had higher optical density means than the microfilled resins; among the evaluated resins, Charisma had the highest optical density means.

Optical density and chemical composition of microfilled and microhybrid composite resins

This study evaluated the optical density of two microfilled and two microhybrid resins, as well as the composition of these materials with regard to their optical density. Cavities prepared in 12 2-mm- or 4-mm-thick acrylic plastic plates were filled with Z250 (3M-ESPE), A110 (3M-ESPE), Charisma (Heraeus-Kulzer) and DurafillVS (Heraeus-Kulzer). The resin increments (2-mm-thick) were light-cured for 40 s. Three 0.12-s radiographic exposures were made of each #2 acrylic plastic plate. DenOptix system optical plates were used to obtain the digital images. Three readings of the composite resin surface were made in each radiograph, totalizing 216 readings. The mean of highest and lowest grey-scale values was obtained. Two specimens of each composite resin were prepared for SEM analysis of the chemical elements related to optical density, using energy dispersive x-ray analysis (EDX). The results were subjected to Shapiro-Wilk's test, ANOVA, Tukey's test at 1 percent level of significance and Pearson's correlation. The mean grey-scale values at 2 mm and 4 mm were: Z250 = 154.27a and 185.33w; A110 = 46.77b and 63.05y; Charisma = 163.40c and 200.46z; DurafillVS = 43.92b and 58.99x, respectively. Pearson's test did not show any positive correlation between optical density and percentage weight of optical density chemical elements. It was concluded that the microhybrid resins had higher optical density means than the microfilled resins; among the evaluated resins, Charisma had the highest optical density means.

Atmospheric pollutants monitoring by analysis of epiphytic lichens.

The Canoparmelia texana epiphytic lichenized fungi was used to monitor atmospheric pollution in the São Paulo metropolitan region, SP, Brazil. The cluster analysis applied to the element concentration values confirmed the site groups of different levels of pollution due to industrial and vehicular emissions. In the distribution maps of element concentrations, higher concentrations of Ba and Mn were observed in the vicinity of industries and of a petrochemical complex. The highest concentration of Co found in lichens from the São Miguel Paulista site is due to the emissions from a metallurgical processing plant that produces this element. For Br and Zn, the highest concentrations could be associated both to vehicular and industrial emissions. Exploratory analyses revealed that the accumulation of toxic elements in C. texana may be of use in evaluating the human risk of cardiopulmonary mortality due to prolonged exposure to ambient levels of air pollution.

Assessment of atmospheric metallic pollution in the metropolitan region of São Paulo, Brazil, employing Tillandsia usneoides L. as biomonitor.

Tillandsia usneoides L. is an epiphytic bromeliad plant able to absorb water and nutrients directly from the air. For this reason this species was selected to carry out a monitoring study of air pollution in the metropolitan region of São Paulo, Brazil. Five consecutive transplantation experiments (8 weeks each) were performed in 10 sites of the city, submitted to different sources of air pollution (industrial, vehicular), using plants collected from an unpolluted area. After exposure, trace metals were analyzed in the plant by instrumental neutron activation analysis. Traffic-related elements such as Zn and Ba presented high concentrations in exposure sites near to heavy traffic avenues (cars, buses and trucks) and may be associated to vehicular sources. For Zn and Co the highest contents were related to industrial zones and can be associated to the presence of anthropogenic emission sources. The rare earth elements, Fe and Rb, probably have soil particles as main source.