[Determination of 24 elements migration in Yixing clay pottery by inductively coupled plasma mass spectrometry].

OBJECTIVE: To establish an analytical method for determining the migration of 24 elements in Yixing clay pottery in 4% acetic acid simulated solution by inductively coupled plasma mass spectrometry. METHODS: Four types of Yixing clay pottery, including Yixing clay teapot, Yixing clay kettle, Yixing clay pot, and Yixing clay electric stew pot, were immersed in 4% acetic acid as a food simulant for testing. The migration amount of 24 elements in the migration solution was determined using inductively coupled plasma mass spectrometry. RESULTS: Lithium, magnesium, aluminum, iron, and barium elements with a mass concentration of 1000 µg/L; Lead, cadmium, total arsenic, chromium, nickel, copper, vanadium, manganese, antimony, tin, zinc, cobalt, molybdenum, silver, beryllium, thallium, titanium, and strontium elements within 100 µg/L there was a linear relationship within, the r value was between 0.998 739 and 0.999 989. Total mercury at 5.0 µg/L, there was a linear relationship within, the r value of 0.995 056. The detection limit of the elements measured by this method was between 0.5 and 45.0 µg/L, the recovery rate was 80.6%-108.9%, and the relative standard deviation was 1.0%-4.8%(n=6). A total of 32 samples of four types of Yixing clay pottery sold on the market, including teapots, boiling kettles, casseroles, and electric stewing pots, were tested. It was found that the migration of 16 elements, including beryllium, titanium, chromium, nickel, cobalt, zinc, silver, cadmium, antimony, total mercury, thallium, tin, copper, total arsenic, molybdenum, and lead, were lower than the quantitative limit. The element with the highest migration volume teapot was aluminum, magnesium, and barium; The kettle was aluminum and magnesium; Casserole was aluminum, magnesium, and lithium; The electric stew pot was aluminum. CONCLUSION: This method is easy to operate and has high accuracy, providing an effective and feasible detection method for the determination and evaluation of element migration in Yixing clay pottery.

Brief Communication: Elemental Models of Primate Nursing and Weaning Revisited.

Objectives: Intra-tooth patterns of trace elements barium (Ba) and strontium (Sr) have been used to infer human and nonhuman primate nursing histories, including australopithecine and Neanderthal juveniles. Here we contrast the two elemental models in first molars (M1s) of four wild baboons and explore the assumptions that underlie each. Materials and Methods: Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was employed to create comprehensive calcium-normalized barium and strontium (Ba/Ca, Sr/Ca) maps of M1 enamel and dentine at 35 micron resolution. Results: Postnatal Ba/Ca values were typically high, peaking ~0.5 years of age and then decreasing throughout M1 crown formation; all four individuals showed minimal Ba/Ca values between ~1.2-1.8 years, consistent with field reports of the cessation of suckling. Enamel Sr/Ca did not support patterns of previous LA-ICP-MS spot sampling as the enamel rarely showed discrete Sr/Ca secretory zonation. Increases in Sr/Ca appeared in coronal dentine beginning ~0.3 years, with varied peak value ages (~0.7-2.7 years) and no evidence of a predicted postweaning decline. Discussion: Inferences of baboon weaning ages from initial Ba/Ca minima are more congruent with behavioral observations than Sr/Ca maxima; this is consistent with studies of captive macaques of known weaning ages. Elemental variation is more apparent in the coronal dentine than the enamel of these baboons, which may relate to its more rapid mineralization and protection from the oral environment. Inferences of nursing histories from enamel Sr/Ca patterns alone should be reconsidered, and elevated values of Ba/Ca and Sr/Ca in teeth formed after weaning require further study.

Correlation of heavy metals' exposure with the prevalence of coronary heart disease among US adults: findings of the US NHANES from 2003 to 2018.

We sought to explore the association between heavy metal exposure and coronary heart disease (CHD) based on data from the US National Health and Nutrition Examination Survey (NHANES, 2003-2018). In the analyses, participants were all aged > 20 and had participated in heavy metal sub-tests with valid CHD status. The Mann-Kendall test was employed to assess the trends in heavy metals' exposure and the trends in CHD prevalence over 16 years. Spearman's rank correlation coefficient and a logistics regression (LR) model were used to estimate the association between heavy metals and CHD prevalence. 42,749 participants were included in our analyses, 1802 of whom had a CHD diagnosis. Total arsenic, dimethylarsonic acid, monomethylarsonic acid, barium, cadmium, lead, and antimony in urine, and cadmium, lead, and total mercury in blood all showed a substantial decreasing exposure level tendency over the 16 years (all Pfor trend < 0.05). CHD prevalence varied from 3.53 to 5.23% between 2003 and 2018. The correlation between 15 heavy metals and CHD ranges from - 0.238 to 0.910. There was also a significant positive correlation between total arsenic, monomethylarsonic acid, and thallium in urine and CHD by data release cycles (all P < 0.05). The cesium in urine showed a negative correlation with CHD (P < 0.05). We found that exposure trends of total arsenic, dimethylarsonic acid, monomethylarsonic acid, barium, cadmium, lead, and antimony in urine and blood decreased. CHD prevalence fluctuated, however. Moreover, total arsenic, monomethylarsonic acid, and thallium in urine all showed positive relationships with CHD, while cesium in urine showed a negative relationship with CHD.

Assessing gestational exposure to trace elements in an area of unconventional oil and gas activity: comparison with reference populations and evaluation of variability.

BACKGROUND: Located in Northeastern British Columbia, the Montney formation is an important area of unconventional oil and gas exploitation, which can release contaminants like trace elements. Gestational exposure to these contaminants may lead to deleterious developmental effects. OBJECTIVES: Our study aimed to (1) assess gestational exposure to trace elements in women living in this region through repeated urinary measurements; (2) compare urinary concentrations to those from North American reference populations; (3) compare urinary concentrations between Indigenous and non-Indigenous participants; and (4) evaluate inter- and intra-individual variability in urinary levels. METHODS: Eighty-five pregnant women participating in the Exposures in the Peace River Valley (EXPERIVA) study provided daily spot urine samples over 7 consecutive days. Samples were analyzed for 20 trace elements using inductively-coupled mass spectrometry (ICP-MS). Descriptive statistics were calculated, and inter- and intra-individual variability in urinary levels was evaluated through intraclass correlation coefficient (ICC) calculation for each trace element. RESULTS: When compared with those from North American reference populations, median urinary levels were higher in our population for barium (~2 times), cobalt (~3 times) and strontium (~2 times). The 95th percentile of reference populations was exceeded at least 1 time by a substantial percentage of participants during the sampling week for barium (58%), cobalt (73%), copper (29%), manganese (28%), selenium (38%), strontium (60%) and vanadium (100%). We observed higher urinary manganese concentrations in self-identified Indigenous participants (median: 0.19 µg/g creatinine) compared to non-Indigenous participants (median: 0.15 µg/g of creatinine). ICCs varied from 0.288 to 0.722, indicating poor to moderate reliability depending on the trace element. SIGNIFICANCE: Our results suggest that pregnant women living in this region may be more exposed to certain trace elements (barium, cobalt, copper, manganese, selenium, strontium, and vanadium), and that one urine spot sample could be insufficient to adequately characterize participants' exposure to certain trace elements. IMPACT STATEMENT: Unconventional oil and gas (UOG) is an important industry in the Peace River Valley region (Northeastern British Columbia, Canada). Information on the impacts of this industry is limited, but recent literature emphasizes the risk of environmental contamination. The results presented in this paper highlight that pregnant women living near UOG wells in Northeastern British Columbia may be more exposed to some trace elements known to be related to this industry compared to reference populations. Furthermore, our results based on repeated urinary measurements show that one urine sample may be insufficient to adequately reflect long-term exposure to certain trace elements.

Review on treatment and utilization of barium slag in China.

Barium slag (BS) is generated as a by-product waste during the production of barium salts from barite. A large amount of BS is discharged annually threating the ecological environment and restricting the development of the barium salts industry. In China, BS is classified as hazardous waste due to its corrosivity, and more importantly because of its extraction toxicity of barium. Soluble barium is toxic and can result in barium poisoning for environment and human beings. The current review presents a detailed summary on general characteristics, discharge and disposal status, harmless treatment pathways and comprehensive utilization of BS in China. BaO, SiO2, CaO, and SO3 occur as main chemical compositions in BS, especially BaO accounting approximately for 35-40%. The mineral compositions include unreacted barite, quartz, clay minerals, newly-formed phases from the side reactions such as BaCO3, BaSiO3 and BaSO3, and residual carbon. A special attention is given to the assessment of the harmless treatment methods for BS from hazardous waste to general waste, which will decrease its management costs. Precipitation and solidification of soluble barium is the common pathway for harmless treatment of BS, and the using of other industrial waste can realize cost-saving. Methods for comprehensive utilization of BS include recovery of barium and carbon, application in building materials, and using as adsorbents for wastewater treatment. In particular, we analyzed and discussed the advantages and disadvantages of these existing process routes, intending to promote potentials for comprehensive utilization of BS in the future.

Occurrence and distribution of heavy metals in water and soil sediments of Vellore District, Tamil Nadu, India.

The occurrence of heavy metals (HMs) in water and soil sediments represents a serious environmental concern. This study revealed the presence and distribution of HMs in water and soil sediments of various places in Vellore District, Tamil Nadu, India. Twenty-one sites were selected along the study area, and inductively coupled plasma-optical emission spectrometry (ICP-OES) was used to analyze the concentration of the heavy metals. The dominance of various HMs in the soil sediment sample follows the order strontium (Sr) > Manganese (Mn) > Barium (Ba) > Zinc (Zn) > Nickel (Ni) and Sr > Mn > Zn > Boron (B) > , respectively. It was found that the concentration of HMs in water and soil sediments in Ambur market and Mottukollai area was significantly higher than the recommended limits. Thus, the results showed that the presence of HMs in water and soil sediments could be threatened pollution factors unsafe for irrigation, drinking, and other human activities.

Spatial distribution and pollution assessment of heavy metals in sediments from the Brahmaputra River watershed in Bangladesh.

Spatial distribution and pollution assessment of selected heavy metals such as barium (Ba), chromium (Cr), nickel (Ni), lead (Pb), vanadium (V), arsenic (As), zinc (Zn), and copper (Cu) in sediments of the Brahmaputra River watershed in Bangladesh was investigated. The mean abundances (ppm) of heavy metals in sediment samples were in decreasing order Ba (375.60) > V (67.60) > Cr (54.10) > Zn (48.20) > Ni (22.28) > Pb (20.25) > Cu (7.59) > As (4.21). Concentrations of Pb and As in the sediments are enriched relative to the average upper continental crust composition, while Ba, V, Cr, Zn, Ni, and Cu decrease considerably. A higher concentration of Pb and Ni indicates that Brahmaputra River watershed samples receive a significant contribution from anthropogenic sources of heavy metals. Chromium displays marked positive correlation with V (r = 0.91, p = < 0.01), inferring a similar source materials input into the watershed. The geo-accumulation index (Igeo) values suggest that the sediments were uncontaminated to moderately contaminated by Ni, Zn, Pb, V, and Cr, whereas moderate to heavily contaminated by As and Cu. The contamination factor (CF) confirmed that sediments in the watershed were moderate to highly contaminated by As, Cu, and Cr. The pollution load index (PLI) values for most of the samples were over one (> 1), indicating an advanced decline in the watershed sediment quality. The overall results of a multivariate statistical analysis suggest that Ba, V, Cr, and Zn contents were all-natural sources, and Pb, Ni, As, and Cu were derived from both natural and anthropogenic sources.

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.

A likelihood-ratio framework for evaluating results of forensic gunshot-residue analysis.

When reporting results of Gunshot Residue (GSR) analysis from a person suspected to be involved in a recent shooting, most forensic experts only provide the court with the raw results (i.e. the number of GSR particles found) and a disclaimer that a positive finding does not prove that the suspect was involved in a firearm shooting incident whilst a negative finding does not prove that he was not. Probabilistic analysis of the GSR results provides more value to the court, so the present study calculated likelihood ratio (LR) values for finding 0-8 characteristic GSR particles (containing Lead, Barium and Antimony) on a suspect's hands, based on the available GSR data from the published literature as well as studies by the authors. Defense propositions, i.e. modes for GSR acquisition other than involvement in a shooting event, were divided into three broad categories: low, medium and heavy background. For each background level and number of GSR particles found, minimal and maximal LR values were calculated. Thus, for each proposition the defense provides for the presence of GSR on the defendant's hands, the forensic expert can provide a possible set of minimal and maximal LR values, leaving the court to examine the defendant's contention and decide which of the three background modes is more plausible according to the circumstances of the specific case.

Laser induced breakdown spectroscopy for the rapid detection of SARS-CoV-2 immune response in plasma.

As the SARS-CoV-2 pandemic persists, methods that can quickly and reliably confirm infection and immune status is extremely urgently and critically needed. In this contribution we show that combining laser induced breakdown spectroscopy (LIBS) with machine learning can distinguish plasma of donors who previously tested positive for SARS-CoV-2 by RT-PCR from those who did not, with up to 95% accuracy. The samples were also analyzed by LIBS-ICP-MS in tandem mode, implicating a depletion of Zn and Ba in samples of SARS-CoV-2 positive subjects that inversely correlate with CN lines in the LIBS spectra.

Designing a novel DNA-based electrochemical biosensor to determine of Ba2+ ions both selectively and sensitively.

This work describes a novel electrochemical biosensor based on G-quadruplex (G4) DNA for the sensitive and selective detection of Ba2+ ions using a Carbon Paste Electrode modified with Ag nanoparticles incorporated in reduced Graphene Oxide via a simple wet chemical method (Ag-rGO/CPE), in the presence of carmoisine (CA) as a new electrochemical indicator. The peak current of CA increased with increasing Ba2+ ions concentration and the DNA-based sensor showed linear ranges of 0.06-0.80 nM and 1.0-80 nM and a Limit of Detection (LOD) of 0.045 nM. The proposed biosensor showed a good selectivity toward Ba2+ ions in the presence of other metal ions such as Ag+, Hg2+, K+ and Na+ and was applied to the analysis of natural samples showing appropriate results.

Elemental profiling of total gunshot residue using total reflection X-ray fluorescence spectrometry.

Gunshot residue (GSR) is a composite of unburnt and partially burnt particles from various components of firearm ammunition cartridges. GSR is customarily sampled from small, localized spots and analyzed visually and elementally. The conventional analytical methods for localized GSR are most commonly done through a paired scanning electron microscope-energy dispersive X-ray spectrometer (SEM-EDS) to look for the presence of lead, barium, and antimony, the inorganic components of ammunition primer. Previous GSR analysis primarily focused on the material deposited on a shooter's hands and used swabbing or adhesive stubs to collect GSR. In this study, total gunshot residue (tGSR) from six types of ammunition was collected from fabric that was shot at a muzzle-to-target distance of 15 cm. Subsequently, each tGSR sample was digested in nitric acid and analyzed with total reflection X-ray fluorescence spectrometry (TXRF). The TXRF technique can simultaneously identify the individual elements in the tGSR and provide absolute elemental quantification. In contrast, EDS scans report the relative elemental compositions of localized GSR samples rather than giving absolute quantitation. This study reliably revealed distinct patterns in six key elements (lead, copper, barium, antimony, iron, and zinc) of tGSR among the ammunition investigated. Elemental profiles were developed from the analyses to represent each ammunition type and the elemental quantities obtained could be used to suggest the category of ammunition that was used.

Noninvasive, visual examination for the presence of gunshot residue on human skin.

When a firearm is discharged, the highest concentration of gunshot residue (GSR) is located on a shooter's hands, forearms, and clothing. Currently, collecting GSR from an individual's hands is accomplished with a carbon disk that is submitted for confirmatory analysis in a forensic laboratory. Presumptive chemical tests can be performed in the field, but these tests consume a portion of the GSR particles leaving a reduced amount of evidence available to be collected and sent to a forensic laboratory. An abundance of research exists for detecting GSR particles instantly on different fabrics using an alternate light source (ALS). This study expanded on that research and developed a noninvasive, visual examination to detect GSR on a suspected shooter's hands without destroying or removing any particles prior to collection. The hands of individuals who recently discharged a firearm were examined under a light source between 475 and 530 nm and an infrared (IR) camera. The fluorescent particles observed on a shooter's hands under 520 nm were similar in size and appearance to GSR particles observed on fabrics under an ALS. The fluorescent particles were collected and analyzed for GSR, and the results indicated that GSR particles were present. More testing needs to be conducted to determine if the fluorescent particles observed are inorganic or organic GSR particles. There is also potential to detect GSR under IR light; however, more research needs to be conducted to determine the composition of the particles observed after image enhancement.

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.

[Metal content and trace elements in groundwater supply of the island of El Hierro (Canary Islands, Spain).] / Contenido de metales y elementos traza en aguas subterráneas de abastecimiento de la isla de El Hierro (islas Canarias, España).

OBJECTIVE: Volcanic eruptions are a natural source of substances potentially dangerous to human health. The island of El Hierro (Canary Islands, Spain) suffered a marine volcanic eruption in 2012, making it necessary to monitor the levels of certain elements that can alter the quality of groundwater supply. The objective of this work was to determine the content of metals and trace elements in the groundwater supply of the Isla del Hierro and to check if they met the quality parameters established in Spanish legislation. METHODS: The content of metals and trace elements (aluminum, lead, cadmium, calcium, potassium, sodium, magnesium, boron, barium, cobalt, chromium, copper, iron, lithium, manganese, molybdenum, nickel, strontium, vanadium, zinc, fluorine) in a total of 60 samples of groundwater supply and agriculture from six different sampling points on the island. The determination was carried out by inductively coupled plasma optical emission spectrophotometry (ICP-OES) and by fluoride ion selective potentiometry. The data were statistically analyzed applying the Kolmogorov-Smirnov test, Levene's statistic, Kruskal-Wallis, Mann-Whitney U, ANOVA and Tukey's test. Significant differences were those that met p<0.05. RESULTS: The highest mean concentration of lead was recorded in the Tigaday samples (0.003±0.0005 mg/L), finding statistically significant differences (p<0.05) in the lead levels between the sampling points. The elements analyzed were below the parametric values set in Royal Decree 140/2003. CONCLUSIONS: The results obtained reflect that, in all the samples analyzed, the quality parameters established in the Spanish legislation (RD 140/2003) are met, being, therefore, waters suitable for human consumption.

OBJETIVO: Las erupciones volcánicas son una fuente natural de sustancias potencialmente peligrosas para la salud humana. La isla de El Hierro (Islas Canarias, España) sufrió una erupción volcánica marina en el año 2012, siendo necesaria la monitorización de los niveles de ciertos elementos que pueden alterar la calidad de las aguas subterráneas de abastecimiento. El objetivo de este trabajo fue determinar el contenido de metales y elementos traza de las aguas subterráneas de abastecimiento de la Isla del Hierro y comprobar si cumplían los parámetros de calidad establecidos en la legislación española. METODOS: Se determinó el contenido de metales y elementos traza (aluminio, plomo, cadmio, calcio, potasio, sodio, magnesio, boro, bario, cobalto, cromo, cobre, hierro, litio, manganeso, molibdeno, níquel, estroncio, vanadio, zinc, flúor) en un total de 60 muestras de agua subterránea de abastecimiento y de agricultura procedentes de seis puntos diferentes de muestreo de la isla. La determinación fue llevada a cabo mediante espectrofotometría de emisión óptica de plasma acoplado inductivamente (ICP-OES) y mediante potenciometría de ion selectivo de fluoruro. Los datos fueron analizados estadísticamente aplicando los tests de Kolmogorov-Smirnov, estadístico de Levene, Kruskal-Wallis, U de Mann-Whitney, ANOVA y test de Tukey. Se consideraron diferencias significativas aquellas que cumplían p<0,05. RESULTADOS: La mayor concentración media de plomo se registró en las muestras de Tigaday (0,003±0,0005 mg/L), encontrándose diferencias estadísticamente significativas (p<0,05) en los niveles de plomo entre los puntos de muestreo. Los elementos analizados se encontraban por debajo de los valores paramétricos fijados en el Real Decreto 140/2003. CONCLUSIONES: Los resultados obtenidos reflejan que, en todas las muestras analizadas, los parámetros de calidad establecidos en la legislación española (RD 140/2003) se cumplen, siendo, por lo tanto, aguas aptas para el consumo humano.

Shells of the bivalve Astarte moerchi give new evidence of a strong pelagic-benthic coupling shift occurring since the late 1970s in the North Water polynya.

Climate changes in the Arctic may weaken the currently tight pelagic-benthic coupling. In response to decreasing sea ice cover, arctic marine systems are expected to shift from a 'sea-ice algae-benthos' to a 'phytoplankton-zooplankton' dominance. We used mollusc shells as bioarchives and fatty acid trophic markers to estimate the effects of the reduction of sea ice cover on the food exported to the seafloor. Bathyal bivalve Astarte moerchi living at 600 m depth in northern Baffin Bay reveals a clear shift in growth variations and Ba/Ca ratios since the late 1970s, which we relate to a change in food availability. Tissue fatty acid compositions show that this species feeds mainly on microalgae exported from the euphotic zone to the seabed. We, therefore, suggest that changes in pelagic-benthic coupling are likely due either to local changes in sea ice dynamics, mediated through bottom-up regulation exerted by sea ice on phytoplankton production, or to a mismatch between phytoplankton bloom and zooplankton grazing due to phenological change. Both possibilities allow a more regular and increased transfer of food to the seabed. This article is part of the theme issue 'The changing Arctic Ocean: consequences for biological communities, biogeochemical processes and ecosystem functioning'.

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

Transport of produced water through reactive porous media.

During hydraulic fracturing (or fracking) large volumes of wastewater (flow-back and produced water) are generated, which are naturally rich in heavy metals and radionuclides, such as radium. Spills may occur during operations and contaminate the groundwater. Therefore, there is an urgent need to identify a practice that can mitigate the negative impact of accidental leaks on water resources. Here, we present an experimental and modeling work on the transport of alkaline earth elements in produced water, which are congeners of radium, namely, barium (Ba2+), strontium (Sr2+), calcium (Ca2+), and magnesium (Mg2+) in addition to sodium (Na+). Column-flood tests were conducted using produced water from a shale-gas site and reactive porous media made of ubiquitous minerals such as sand, hydrous ferric oxide, activated alumina, and manganese oxide. In all cases, no retardation of the ions was observed at the salinity conditions of the produced water, but strong retardation in the pH front was measured, indicating that adsorption indeed occurred. When using manganese oxide and upon dilution of produced water, the concentration fronts of all major divalent cations were retarded. However, a fast wave of solute, traveling at the average flow velocity, emerged. This phenomenon confirmed that significant adsorption occurred under those conditions. But, pH-dependent adsorption and hydrodynamic dispersion favored fast solute transport. Overall, these results suggest that manganese oxide could be used as a reactive material in the lining of temporary storage tanks and in the well cases in order to retard the migration of the major toxic elements in produced water. However, mixing must be controlled to avoid the emergence of an instability at the concentration fronts favoring the formation of fast waves.

Reactive transport modeling of produced water disposal into dolomite saline aquifers: Controls of barium transport.

Experimental results on barium transport in dolomite are used to formulate, calibrate, and validate a reactive transport model of produced water disposal into dolomite saline aquifers. The model accounts for sorption, dissolution/precipitation reactions of minerals (dolomite, calcite, barite, gypsum, and witherite) and complexation and acid-base reactions of most abundant ionic species (H+, HCO3-, SO42-, Ca2+, Mg2+, and Cl-) in produced waters including Ba2+ which is the most common and abundant heavy metal present in produced water from oil and gas reservoirs. The model is applied to determine the chemical controls of barium transport in Arbuckle dolomite aquifers. The simulated scenario corresponds to produced water disposal through a Class II injection well located near an abandoned well that can facilitate the transport of barium to underground sources of drinking water (USDW). Simulation results reveal that most suitable dolomite aquifers to prevent the contamination of USDW by barium are dolomite aquifers of high SO42- content (>1000 mg/L). The mobility of barium which is promoted by the formation of Ba(Cl)+ and competition of cations (Ca2+ and Mg2+) for hydration sites of dolomite can be suppressed by the precipitation of barium as barite in dolomite saline aquifers of high SO42- content. A sensitivity analysis conducted using a two-level factorial design of experiments indicates that barium transport can be controlled by the initial concentration of a single ionic specie (mostly SO42-) or the concentration of various ionic species (e.g., SO42-, Cl-, and Mg2+). This depends on the chemical composition of both the dolomite saline aquifer and injection produced water. This work highlights the potentiality of a reactive transport simulation approach to conduct compatibility analysis of dolomite saline aquifers and produced waters to select dolomite aquifers and/or decide on treatment methods to prevent the contamination of USDW by barium.