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Clay minerals are effective adsorbents used for the remediation of toxic heavy metals from wastewater due to their large surface areas and great cation-exchange capacities. In this study, the removal of lead ions from aqueous solutions via adsorption was investigated using raw and iron-modified Turkish sepiolite. The aim of this study was to examine the effects of modification and environmental conditions on the sorptive properties of sepiolite samples. Initially, the raw sepiolite (Sep) and magnetic sepiolite/Fe2O3 composite (MagSep) prepared using the co-precipitation method were characterized via mineralogical and petrographical means and the physicochemical properties were determined. Then, the batch adsorption of lead (Pb2+) ions on the sepiolite samples was examined under various conditions (solution pH, adsorbent dosage, contact time, initial Pb2+ ion concentration, temperature, shaking rate). The adsorption capacity of MagSep was found to be greater than that of Sep under all experimental conditions. The results showed that the adsorption process followed a pseudo-second-order kinetic model, and the Langmuir isotherm best correlated with the experimental data. The maximum adsorption capacities were found to be 60.6 and 90.1 mg g–1 for Sep and MagSep, respectively. The characterization of the Pb-adsorbed sepiolite samples showed that lead formed covalent bonds with the sepiolite samples and attached to the sepiolite surface mainly through ion exchange. MagSep can be used efficiently in the field of wastewater treatment for the removal of Pb2+ ions as it does not release any toxic pollutants and can be separated easily with the use of a magnetic field.
The small finds discovered during the 1948–1951 excavations by Katherine M. Kenyon and John B. Ward-Perkins at Sabratha were scattered after the 1950s and have taken some time to be re-assembled. The following report on the small objects includes material in silver, copper alloy, iron, lead, glass, semiprecious stones, clay and stone, with a separate report on the substantial bone artefact assemblage. As well as providing the basic data on the objects, some of which are unique to Roman Libya, efforts have been made to put them into their Empire-wide context.
The excavation of a palaeochannel at the Vistre de la Fontaine 2-2 archaeological site, 3 km downstream from the ancient city of Nîmes (southeastern France), provided an accumulation sequence covering the last 2,500 years. Trace metal analyses of these alluvial sediments disclosed lead (Pb) contamination during the Early Roman Empire, with concentrations close to 1,000 ppm, a factor of 100 above the local geochemical background. This excess of Pb shows a uniform isotopic signature that may reflect unchanged ore sources, perhaps from the Massif Central or from Great Britain. The Pb peak accompanied visible waste that was transported in the sediments of the Vistre de la Fontaine at the time of the development of the Nîmes urban water supply and drainage network during the Early Roman Empire. This research shows the bimillennial persistence of palaeo-contamination in a peri-urban alluvial plain and the relevance of fluvial sedimentary archives in documenting ancient waste.
Immunological and oxidative alterations have been reported around calving in dairy cattle. In addition, the levels of heavy metals rise in the blood around parturition, which might affect body systems. Therefore, in this Research Communication we evaluate the changes in whole blood lead (Pb), arsenic (As), and cadmium (Cd) around calving, in comparison with the beginning of the dry period, and assess the correlations of these elements with immunological factors and oxidative markers. Samples were collected from 30 clinically healthy dairy cows in the early dry period (−6 w), one week before expected calving (−1 w), and one week postpartum (+1 w). The highest concentrations of Pb, As, and Cd were observed at −1 w and all the three elements decreased after parturition leading to significantly lower As and Cd, compared to −1 w (P < 0.05). The lowest levels of tumor necrosis factor-alpha, immunoglobulin G, interleukin 4, interleukin 10 and haptoglobin were found at −1 w simultaneous with the highest measures of the heavy metals, with tumor necrosis factor-alpha being significantly lower at this time (P < 0.05). At −6 w, As concentration was significantly (P < 0.05) correlated negatively (r = −0.366) and positively (r = 0.417) with total antioxidant capacity and malondialdehyde, respectively. Furthermore, at −1 w Pb and As had significant (P < 0.05) negative correlations with interferon gamma (r = −0.502) and interleukin 4 (r = −0.483), respectively. After parturition, Pb was observed to be negatively correlated with total antioxidant capacity (r = −0.538, P < 0.05). The observed results revealed that the alterations in immunological factors and antioxidant capacity around parturition were correlated with Pb and As levels.
Beneficial effects of human-animal contact on human health have contributed to the wide distribution of animal-assisted interventions (AAIs). While considerable effort has been devoted to the study of human welfare during AAIs, potential effects on therapy animals have been addressed less frequently. The aim of this study was to determine baseline and work-related levels of cortisol, a glucocor-ticoid hormone that mediates physiological responses to arousal, in certified therapy dogs and therapy dogs in training. All dogs (n = 21) participated in weekly group-AAIs in adult mental healthcare. Saliva samples were collected over the course of AAIs and on non-working days and analysed with a cortisol enzyme immunoassay. Analysis of the results revealed that according to their cortisol responses, both therapy dogs and therapy dogs in training were not stressed by AAIs. However, cortisol levels during work in certified therapy dogs performing AAIs on- and off-lead varied significantly, suggesting that further investigation into the use of a lead or other methods of giving therapy dogs opportunities to approach or avoid human contact is needed.
This work elucidated the performance and mechanisms of Pb2+ adsorption by kaolinite, montmorillonite, goethite and ferrihydrite using batch experiments. The contributions of various adsorption mechanisms were quantified using a stepwise extraction method. Several characterizations (scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, point of zero charge analysis and X-ray fluorescence) were utilized to analyse the physicochemical properties and the potential adsorption mechanisms. The results indicated that the adsorption processes of montmorillonite and goethite approached equilibrium within 20 min, while 60 min were required for the adsorption processes of kaolinite and ferrihydrite. The adsorption processes of Pb2+ by the four minerals best fit the pseudo-second order model. The adsorption capacities of the four minerals for Pb2+ followed the order: montmorillonite > goethite > ferrihydrite > kaolinite, and the maximum adsorption capacities were 69.20, 46.95, 34.32 and 18.62 mg g–1, respectively. The stepwise extraction test showed that the adsorption mechanism of Pb2+ was dominated by ion exchange for montmorillonite, precipitation and complexation for goethite and complexation for kaolinite and ferrihydrite.
New product development processes need to be compliant to regulatory requirements, and this chapter highlights the salient processes and quality systems to put into place to achieve success. Project management is made simple with specific tools provided here. Customer feedback is channeled into specific product characteristics, and the right tools are shown in this chapter. The biopharma industry has statistics showing less than 10% of starting compounds succeed in reaching market approval, and this chapter explains what causes these failures. The key issues that have repeatedly caused failure during device and diagnostic product development are also pointed out. Ethical decisions have to be made during product development as shown in this chapter. Outsourcing is a real option due to the availability of many contract research and manufacturing organizations, and judicious use of this option is discussed in this chapter. Key milestones that reduce risk and show transition from early stage to preclinical prototype stages are reviewed here. Does the popular concept of minimum viable product in software development apply in biomedicine prototyping? Other similar questions that help the reader understand pitfalls and best practices are answered here.
Lead as an industrial pollutant can be detected at all stages of the working and living environment. Lead, based on its properties, solubility and mobility, accumulates in the soil, so that the average concentrations of oil in the soil are between 15 and 25 mg/kg (Radojević at all., 1999). Due to increased human activity, the amount of copper in the air, soil and water has increased. Glutathione (GSH) is an essential cofactor of many enzymes, such as: formaldehyde dehydrogenase, glyoxalase, prostaglandin endoperoxide isomerase, dehydrochlorinase and others. GSH is a biological redox in the metabolism of erythrocytes, it also plays a role in the transport of amino acids. Reactive forms of oxygen cause oxidative biomolecules (lipids, proteins, DNA) (Freidovich, 1999; Massaad i Klann, 2010).
The aim of this research was to examine the protective role of supplements GSH in conditions of chronic intoxication with sublethal doses of lead acetate and copper II sulfate.
The preparation of biomaterials for testing and making homogenates of brain tissue of albino rats of Wistar strain was performed and the activity of acid and alkaline DNase was measured spectrophotometrically (Kocić i sar., 1998).
Lead otherwise “as soft Lewis acid” has a pronounced affinity for interaction with “soft bases” such as S-atoms of the thiol group in antioxidants, natural biomolecules and supplements in this case in glutathione.
It can be said that GSH is a desirable supplement and antioxidant in the detoxification of reactive oxygen species in rats exposed to lead poisoning.
As, Pb and Hg are common environmental contaminants in low- and middle-income countries. We investigated the association between child toxicant exposure and growth and development and determined if this association was mitigated by Se concentration. Toxicant concentrations in fingernail samples, anthropometry and Bayley’s Scales of Infant Development, 3rd edition domains were assessed in 36-month-old children whose mothers had been part of a randomised controlled trial in rural Vietnam. Multivariable regression analyses were performed to estimate the effect of toxicant exposure on clinical outcomes with adjustments for potential confounders and interaction with fingernail Se concentration. We analysed 658 children who had data for at least one physical or developmental outcome, and at least one toxicant measurement, and each of the covariates. Fingernail As concentration was negatively associated with language (estimate per 10 % increase in As: −0·19, 95 % CI: (–0·32, −0·05)). Pb was negatively associated with cognition (estimate per 10 % increase in Pb: −0·08 (–0·15, −0·02)), language (estimate per 10 % increase in Pb: −0·18 (–0·28, −0·10)) and motor skills (estimate per 10 % increase in Pb: −0·12 (–0·24, 0·00)). Hg was negatively associated with cognition (estimate per 10 % increase in Hg: −0·48, (–0·72, −0·23)) and language (estimate per 10 % increase in Hg −0·51, (–0·88, −0·13)) when Se concentration was set at zero in the model. As Se concentration increased, the negative associations between Hg and both cognition and language scores were attenuated. There was no association between toxicant concentration and growth. As, Pb and Hg concentrations in fingernails of 3-year-old children were associated with lower child development scores. The negative association between Hg and neurological development was reduced in magnitude with increasing Se concentration. Se status should be considered when assessing heavy metal toxicants in children and their impact on neurodevelopmental outcomes.
To determine the association between hearing loss and environmental Pb, Cd and Se exposure, a total of 1503 American adults from National Health and Nutrition Examination Survey (NHANES) (2011–2012) were assessed. The average of four audiometric frequencies (0·5, 1, 2 and 4 kHz) was used to identify speech-frequency hearing loss (SFHL), while the average of 3 audiometric frequencies (3, 4 and 6 kHz) was used to identify high-frequency hearing loss (HFHL). HFHL adjusted OR determined by comparing the highest and lowest blood Pb and Cd quartiles were 1·98 (95 % CI: 1·27, 3·10) and 1·81 (95 % CI: 1·13, 2·90), respectively. SFHL was significantly associated with blood Cd with the OR = 2·42 for the highest quartile. When further stratified by age, this association appeared to be limited to adults aged 35–52 years. After stratified by gender, except for Pb and Cd, we observed that blood Se showed a dose-dependent association with SFHL in men. In women, only Cd showed a dose-dependent association with speech and high-frequency hearing loss. Hearing loss was positively associated with blood levels of Pb and Cd. Additionally, our study provided novel evidence suggesting that excessive Se supplement would increase SFHL risk in men.
A negative association between blood Pb level (BPbL) and vitamin D metabolites in occupationally exposed populations has been reported, but data from the general population are scarce. Furthermore, the association between BPbL and vitamin D binding protein (DBP) and free 25-hydroxyvitamin D (25(OH)D) has not been reported. We investigated the association of BPbL with DBP, total and free 25(OH)D in healthy adolescents (n 1347; age range 11–16 years) cross-sectionally selected from all Governorates of Kuwait, utilising multi-stage cluster random sampling. Pb in whole blood was analysed by inductively coupled plasma MS, and DBP with ELISA. Plasma 25(OH)D was analysed by LC-MS/MS, and free 25(OH)D was calculated utilising the levels and binding affinities of DBP and albumin for 25(OH)D. DBP was positively associated with BPbL (β = 0·81; 95 % CI 0·14, 0·22; P < 0·001). A negative association between BPbL and total 25(OH)D was non-significant (P = 0·24) when BPbL was used as a continuous variable but was significant when used as quartiles (P = 0·02). The negative association between BPbL and free 25(OH)D was significant whether BPbL was used as continuous, as quartiles or as cut-off point of <5 µg/dl (0·24 µmol/l). In multinomial logistic regression, the odds of vitamin D insufficiency and deficiency were more than two-fold higher in the upper quartiles of BPbL compared with the lowest quartile. The negative correlation of BPbL with free 25(OH)D was more robust than its correlation with total 25(OH)D. Future studies must consider the levels of DBP when assessing the association between Pb and vitamin D metabolites.
Kufahrite, PtPb, is a new mineral (IMA2020-045) from the Ledyanoy Creek placer, Koryak Highlands, Russia. The mineral was found in isoferroplatinum (Pt3Fe) grains extracted from a heavy-mineral concentrate, together with tetraferroplatinum (PtFe), tulameenite (Pt2FeCu), native iridium, hollingworthite (RhAsS) and Cr-rich spinel. Kufahrite occurs as part of alteration rims which are formed together with tetraferroplatinum after isoferroplatinum, or as grains up to 150 μm in size. According to powder X-ray diffraction analyses kufahrite is isotypic to its synthetic analogue, it is hexagonal and crystallises in space group P63/mmc adopting the nickeline structure type. Its unit-cell parameters are: a = 4.2492(6) Å; c = 5.486(6) Å; V = 85.78 Å3 and Z = 2. The calculated density is 14.80 g/cm–3. The strongest diffraction lines are [d, Å (I, %) (hkl)]: 3.052 (80) (101), 2.197 (100) (102), 2.125 (28) (110), 1.747 (18) (210), 1.528 (35) (202), 1.240 (18) (212) and 0.958 (22) (312). The Vickers hardness is 295 kg/mm2 (range 262–320, n = 5), corresponding to a Mohs hardness of 4. The empirical formula of kufahrite, calculated from a mean value of 23 electron-microprobe analyses is (Pt0.94Rh0.04)Σ0.98(Pb0.83Sb0.19)Σ1.02. The name (pronounced as [ku fa rait]) honours Fahrid Shakirovitch Kutyev (1943‒1993), a geologist from the Institute of Volcanology of USSR Academy of Sciences, who played a key role in the discovery of the Koryak–Kamchatka Platinum Belt, including the Ledyanoy Creek placer platinum deposit, where the new mineral has been discovered.
High-resolution analysis of the ice core from Colle Gnifetti, Switzerland, allows yearly and sub-annual measurement of pollution for the period of highest lead production in the European Middle Ages, c. AD 1170–1220. Here, the authors use atmospheric circulation analysis and other geoarchaeological records to establish that Britain was the principal source of that lead pollution. The comparison of annual lead deposition at Colle Gnifetti displays a strong similarity to trends in lead production documented in the English historical accounts. This research provides unique new insight into the yearly political economy and environmental impact of the Angevin Empire of Kings Henry II, Richard the Lionheart and John.
Despite evidence for the effects of metals on neurodevelopment, the long-term effects on mental health remain unclear due to methodological limitations. Our objective was to determine the feasibility of studying metal exposure during critical neurodevelopmental periods and to explore the association between early-life metal exposure and adult schizophrenia.
We analyzed childhood-shed teeth from nine individuals with schizophrenia and five healthy controls. We investigated the association between exposure to lead (Pb2+), manganese (Mn2+), cadmium (Cd2+), copper (Cu2+), magnesium (Mg2+), and zinc (Zn2+), and schizophrenia, psychotic experiences, and intelligence quotient (IQ). We reconstructed the dose and timing of early-life metal exposures using laser ablation inductively coupled plasma mass spectrometry.
We found higher early-life Pb2+ exposure among patients with schizophrenia than controls. The differences in log Mn2+ and log Cu2+ changed relatively linearly over time to postnatal negative values. There was a positive correlation between early-life Pb2+ levels and psychotic experiences in adulthood. Moreover, we found a negative correlation between Pb2+ levels and adult IQ.
In our proof-of-concept study, using tooth-matrix biomarker that provides direct measurement of exposure in the fetus and newborn, we provide support for the role of metal exposure during critical neurodevelopmental periods in psychosis.
The complex processes that underlie normal nervous system development are known to be extremely vulnerable to perturbation by chemicals that are present in the human environment, either naturally or as a result of human activities. These processes include neurogenesis, differentiation and migration of neurons, myelination, and synaptogenesis. Children are generally at greater risk than adults of suffering adversities from chemical exposures because of their physiology and behavior. As a result, reductions in cognitive function, including intelligence, are among the most important effects of such exposures. This chapter surveys the harmful impacts on children’s brains and cognition of certain chemicals and chemical classes, including mercury, lead, organophosphate pesticides, air pollution, synthetic organic compounds (e.g., flame retardants, plastics), and compounds that disrupt the endocrine system. The final section illustrates how an exposure that causes relatively modest cognitive morbidity in an individual can nevertheless, if highly prevalent as many chemical exposures are, contribute substantially to the burden of disease at the population level.
A bentonite sample from the Petreş ti deposit, Cluj County (Romania), was used to remove heavy-metal ions (Cd2+, Pb2+, Cr3+) from wastewaters. A representative sample of bentonite (P) was characterized using the Brunauer-Emmett-Teller (BET) method, wet chemical analyses, X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy. The bentonite deposit from Petreş ti is present at the contact between Upper Jurassic limestones and basaltic andesites with subordinate basalt bodies. These rocks are composed of clay minerals (mainly smectite), with opal, quartz, feldspar and mica/illite as minor phases. The bentonite sample was used in powdered form (d < 0.2 mm) without any chemical treatment. The influence of the working regime, static and dynamic, on the process efficiency was studied using monocomponent synthetic wastewaters containing Cd, Pb and Cr ions. The bentonite sample proved to be efficient for the removal of these heavy-metal ions; removal efficiencies up to 100% (lead removal) were achieved.
Daliranite, ideally PbHgAs2S6, a new sulphosalt from the Zarshouran Au-As deposit, Takab region, Iran, occurs as a rare sulphosalt species at the Carlin-type Zarshouran Au-As deposit North of the town of Takab in the Province of West Azarbaijan, Iran. The new species is associated with orpiment, rarely with galkhaite, hutchinsonite and cinnabar. The strongly silicified matrix of the specimens has veinlets of sphalerite, with rare inclusions of galena and various (Cu)-Pb-As(Sb) sulphosalts. Daliranite occurs as matted nests of acicular and flexible fibres up to 200 μm in length and a width less than a few μm. The colour is orange-red with a pale orange-red streak and the lustre is adamantine. The mineral is transparent and does not fluoresce. The Mohs hardness is <2. Electron microprobe analyses give the empirical formula Pb0.95Tl0.01Hg1.04As2.10S5.91, ideally PbHgAs2S6, a new sulphosalt from the Zarshouran Au-As deposit, Takab region, Iran; the calculated density is 5.93 g cm–3. Unit-cell parameters were determined by an electron-diffraction study and refined from X-ray powder data. Daliranite is monoclinic primitive with a = 19.113(5) Å, b = 4.233(2) Å, c = 22.958(8) Å, β = 114.78(5)°, V = 1686.4 Å3 and Z = 8, a:b:c = 4.515:1:5.424, space group P2, Pm or P2/m. The strongest X-ray powder-diffraction lines [d in Å, (I), (hkl)] are: 8.676, (80), (200); 4.654, (50), (401); 3.870, (40), (211); 3.394, (50), (113); 3.148, (40b), (602); 2.892, (50), (600); 2.724, (100), (703); 2.185, (50), (319). The formula shows a sulphur excess which may correspond to S—S bonding (persulphide). The new sulphosalt is a late phase in the crystallization sequence, and was formed after orpiment, contemporaneously with quartz II, at a temperature between 157 and 193°C. The name honours Dr Farahnaz Daliran (University of Karlsruhe, Germany) in recognition of her outstanding contributions to research on ore deposits, especially Au, Zn and Fe, in Iran.
The Mathiatis massive sulphide deposit in Cyprus was a low-grade (0.3% Cu), three million ton ore body of pyrite and minor chalcopyrite occurring within basaltic lavas of the Troodos ophiolite. Cessation of mining in 1987 left a deep open pit surrounded by large heaps of spoil, which are undergoing oxidation and leaching. The aim of this study was to determine the mineralogical controls on the storage and potential remobilization of As, Cu, Pb and Zn within, and from, mine spoil heaps. Most of the spoil samples collected, and related materials (stream sediment, reaction zone between a boulder of massive pyrite and calcareous chert, salt crusts on stream beds), are enriched in As (27—220 ppm), Cu (110—400 ppm), Pb (10—140 ppm) and Zn (290—12,000 ppm) relative to both the basalt and calcareous chert (As 4—10 ppm, Cu 20—76 ppm, Pb 3—6 ppm, Zn 39—200 ppm).
Arsenic, Cu, Pb and Zn in the spoil and related materials are associated with Fe(-Al-S)-O, Fe(-Al-Mg)-S-O, Al(-Mg-Fe)-S-O and Mg(-Al-Fe)-S-O phases (the brackets represent minor components of less than 20 wt.% within the phases). Chemical extraction work using CaCl2 suggests that Cu, Zn and to some extent, As, are potentially more soluble than Pb. This is corroborated by the very high total concentrations of Cu and Zn in both the secondary salt crusts and the reaction zone material, high CaCl2-extractable As, Cu and Zn in the salt crusts, and aqueous data for the Mathiatis mine area collected for a European Union LIFE report. This may have implications for ecosystem health and water quality in the Mathiatis area and areas of similar mineralogy and climate world wide.