A significant area of late Neoproterozoic–early Cambrian seafloor hosted a ferruginous to euxinic condition as a result of expanded primary productivity-driven pumping of organic matter into subsurface water column and weak water column mixing in the concomitant sea. However, the cause and extent of increased marine primary productivity during this time interval remain unknown. To estimate the primary productivity in a late Neoproterozoic sea, this study investigated the Sirbu Shale, Vindhyan Supergroup, for trace elements, organic carbon isotopes and total organic carbon (TOC). Among the trace elements, cadmium (Cd), known for extremely low concentration in crustal rocks but higher abundance in biogenic organic matter, was the key parameter in the palaeoproductivity estimation. The Cd enrichment in the Sirbu Shale samples is comparable to that in modern marine sediments of the oxygen minimum zones in Chilean margins, Arabian Sea and Gulf of California characterized by high primary productivity and seasonal upwelling. In terms of Cd enrichment, the lower section of the Sirbu Shale was deposited under suboxic conditions, while the upper section was deposited under a relatively less reducing condition. Cd/Mo ratios > 0.36 in the shale sample indicate that the palaeoproductivity was strongly influenced by the nutrient supply through sea-shelf upwelling. Using non-detrital enrichment of Cd in Sirbu Shale samples, we calculated that the TOC exported to the floor of Sirbu Shale palaeodepositional setting through primary productivity ranged from 0.71 to 10.16%.

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.

Argentotetrahedrite-(Cd), Ag6(Cu4Cd2)Sb4S13, has been approved as a new mineral species by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association using samples from Rudno nad Hronom, Slovak Republic. It occurs as anhedral grains up to 30 μm in size, steel-grey to black in colour, with a metallic lustre, in association with greenockite and other tetrahedrite-group minerals [argentotetrahedrite-(Zn) and tetrahedrite-(Zn)], earlier base-metal minerals, Ag sulfides and sulfosalts (acanthite, pyrargyrite and polybasite) and later galena. Argentotetrahedrite-(Cd) is isotropic, grey in colour, with a creamy tint and rapidly (tens of minutes) tarnishes to orange–brown. Reflectance data for Commission on Ore Mineralogy (COM) wavelengths in air are [λ (nm), R (%)]: 470, 30.4; 546, 30.3; 589, 30.3; and 650, 28.7. The chemical formula of the samples studied, recalculated on the basis of ΣMe = 16 atoms per formula unit, is: (Ag3.28Cu2.72)Ʃ6.00[Cu4(Cd1.68Fe0.27Zn0.16)]Ʃ6.11(Sb3.71As0.15)Ʃ3.86S12.79. Argentotetrahedrite-(Cd) is cubic, I$\bar{4}$3m, with a = 10.65(2) Å, V = 1208(4) Å3 and Z = 2. Argentotetrahedrite-(Cd) is isotypic with other members of the tetrahedrite group. The structural relationship between argentotetrahedrite-(Cd) and other members of the freibergite series are discussed and previous findings of this species are briefly reviewed.

Tennantite-(Cd), Cu10Cd2As4S13, was approved as a new mineral species from the Berenguela mining district, Pacajes Province, La Paz, Bolivia. It occurs as black metallic anhedral grains, up to 1 mm across, associated with baryte, montmorillonite and secondary Cd-sulfates (aldridgeite, niedermayrite and voudourisite). In reflected light, tennantite-(Cd) is isotropic and grey with brownish tints. Reflectance data for the four COM wavelengths in air are [λ (nm): R (%)]: 470: 30.0; 546: 30.1; 589: 28.2; and 650: 25.8. Electron microprobe analysis gave (in wt.% – average of 11 spot analyses): Cu 40.56(32), Ag 0.05(5), Fe 0.04(1), Zn 1.91(63), Cd 11.32(1.09), Hg 0.04(7), As 19.04(43), S 26.78(30), total 99.74(53). On the basis of ΣMe = 16 atoms per formula unit (apfu), the empirical formula of tennantite-(Cd) is Cu9.98Ag0.01Cd1.57Zn0.46Fe0.01As3.97S13.05. Tennantite-(Cd) is cubic, I$\bar{4}$3m, with unit-cell parameters a = 10.3088(2) Å, V = 1095.53(6) Å3 and Z = 2. Its crystal structure was refined by single-crystal X-ray diffraction data to a final R1 = 0.0152 on the basis of 359 unique reflections with Fo > 4σ(Fo) and 22 refined parameters. Tennantite-(Cd) is isotypic with other tetrahedrite-group minerals. Its crystal-chemistry is discussed and previous findings of Cd-rich tetrahedrite-group minerals are briefly reviewed.

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.

Cadmium (Cd) is a toxic heavy metal that poses a threat to the health of humans and animals. It can cause serious damage to the small intestine, which is the main absorption site of Cd and the primary target organ after oral administration. Our previous study found that zinc chelate of hydroxy analogue of methionine (Zn-HMTB), a new type of feed additive, decreased Cd accumulation in the liver and kidneys. The aim of this study was to investigate the effect of Zn-HMTB on Cd absorption and Cd-induced toxicity in the small intestine of piglets. Twenty-four piglets (Landrace × Large White, 13.22 ± 0.58 kg BW) were randomly divided into four dietary treatment groups: basal diet, and diets containing 30 mg/kg Cd from CdCl2 and 0, 100 or 200 mg/kg Zn from Zn-HMTB. The experiment lasted 27 days. The feed intake and final BW of each piglet were recorded at the end of the experiment. Gastrointestinal (GI) tract tissue and samples of liver, kidney, spleen, heart, lung and longissimus muscle tissue and faeces were collected. The concentrations of Cd and metal trace elements in the GI tract and organs were analysed, as was the relative messenger RNA (mRNA) expression of inflammatory cytokines and metal element transporters in the small intestine, and epithelial apoptosis in the small intestine. The results showed that, compared with Cd-treated piglets, piglets in the Zn-HMTB and Cd cotreatment groups had less Cd deposition in the stomach, ileum, caecum, colon, liver, kidneys, spleen, lungs, heart and muscles (P < 0.05), and lower Cd concentrations in faeces (P < 0.05), suggesting that Zn-HMTB increased Cd absorption and the excretion of Cd in other forms (possibly urine). Zinc chelate of hydroxy analogue of methionine increased Zn deposition in the jejunum and the relative mRNA expression of divalent metal transporters 1 and zinc transporter 5 in the duodenum (P < 0.05), indicating that Zn-HMTB may promote the absorption and transportation of Cd and Zn together by upregulating metal element transporters. Competition between Zn and Cd may be responsible for accelerating Cd excretion. Furthermore, Zn-HMTB reduced Cd-induced apoptosis of enterocytes and inflammatory stimuli in the small intestine, suggesting that Zn-HMTB reduced Cd-induced toxicity to the small intestine. These results suggest that Zn-HMTB can be helpful in decreasing Cd accumulation in the GI tract and organs of piglets and relieving Cd-induced toxicity to the small intestine but cannot reduce the absorption of Cd.

Sphalerite is the main source of In – a ‘critical’ metal widely used in high-tech electronics. In this mineral the concentration of In is commonly correlated directly with Cu content. Here we use X-ray absorption spectroscopy of synthetic compounds and natural crystals in order to investigate the substitution mechanisms in sphalerites where In is present, together with the group 11 metals. All the admixtures (Au, Cu, In) are distributed homogeneously within the sphalerite matrix, but their structural and chemical states are different. In all the samples investigated In3+ replaces Zn in the structure of sphalerite. The In ligand distance increases by 0.12 Å and 0.09–0.10 Å for the 1st and 2nd coordination shells, respectively, in comparison with pure sphalerite. The In–S distance in the 3rd coordination shell is close to the one of pure sphalerite. Gold in synthetic sphalerites is coordinated with sulfur (NS = 2.4–2.5, RAu–S = 2.35 ± 0.01 Å). Our data suggest that at high Au concentrations (0.03–0.5 wt.%) the Au2S clusters predominate, with a small admixture of the Au+ solid solution with an Au–S distance of 2.5 Å. Therefore, the homogeneous character of a trace-element distribution, which is commonly observed in natural sulfides, does not confirm formation of a solid solution. In contrast to Au, the presence of Cu+ with In exists only in the solid-solution state, where it is tetrahedrally coordinated with S atoms at a distance of 2.30 ± 0.03 Å. The distant coordination shells of Cu are disordered. These results demonstrate that the group 11 metals (Cu, Ag and Au) can exist in sphalerite in the metastable solid-solution state. The solid solution forms at high temperature via the charge compensation scheme 2Zn2+↔Me++Me3+. The final state of the trace elements at ambient temperature is governed by the difference in ionic radii with the main component (Zn), and concentration of admixtures.

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.

Changes in the lability and local environment of Cd sorbed onto calcite, hydroxylapatite and humic acid have been investigated as a function of time (30 min–9 months) using a combination of X-ray adsorption spectroscopy (XAS) and isotopic dilution techniques with Cd concentrations between 1 and 1000 mmol kg –1. Enhanced X-ray absorption fine structure (EXAFS) shows that precipitation of Cd carbonate was initially observed on calcite. Ageing of a 10 mmol kg–1 sample showed replacement of Cd in the fourth shell with Ca, indicating diffusion between the two phases had occurred. This diffusion appeared to be ongoing for a 10 mmol kg–1 sample even after 9 months of reaction. Only 20% of the Cd in a sample with 10 mmol kg–1 Cd remained labile after 6 months of reaction, suggesting a high degree of incorporation into the solid phase, in agreement with the XAS results. The XAS results for hydroxylapatite indicated that Cd is not fixed in the mineral lattice and Cd lability in a sample loaded with 10 mmol kg–1 Cd was ∼55% after 6 months of reaction. This indicates that a relatively high proportion of the Cd sorbed to hydroxylapatite remained as kinetically active surface species. Little change was observed in the local environment of Cd adsorbed on flocculated Ca-humate samples as a function of time and ∼75% of the Cd remained radio-labile after 6 months of reaction regardless of initial Cd loading. High lability is expected because incorporation into a solid matrix or surface precipitation of a Cd phase is less likely than with the mineral phases.

We have applied atomistic simulation techniques to model the continuous CdCO3-CaCO3 solid solution and to investigate the thermodynamic properties. All inequivalent substitutional configurations were considered for the single unit cell and the (2x1x1) supercell for the full range of Cd concentrations, as well as doping between 0and 16.7 mol.% Cd for the (2x2x1) supercell. Our calculations show that segregation of Cd2+ and Ca2+ is energetically favourable when compared with any other cation distribution. No cation ordering is expected at high temperature and the system behaves as an ideal solid solution above 200 K, due to the configurational entropy. The lattice parameters change with the Cd concentration, where they are predicted to follow a linear relationship, due only to cation substitution but not cation ordering.

Cadmium sulfide mineralization occurs in grey-black shales of the late Mesoproterozoic Stoer Group, Torridonian Supergroup, northwest Scotland. Cadmium is strongly redox-controlled, and normally concentrated in anoxic marine sediments or epigenetic mineralization involving organic matter. However the Stoer Group was deposited in a terrestrial environment, including lacustrine deposits of shale. At the limited levels of atmospheric oxygenation in the Mesoproterozoic (∼10% of present), the near-surface environment could have fluctuated between oxic and anoxic, allowing fractionation of Cd from Zn, and the formation of Cd sulfide rather than Cd-bearing sphalerite. This occurrence emphasizes the importance of the Stoer Group as a record of the Mesoproterozoic terrestrial environment.

The use of optical absorption spectroscopy for the study of the changes in local distortions during phase transformations is discussed, with particular reference to the P213-P212121 transition in K2Co2(SO4)3 langbeinite. In order to extend this technique to the study of cobalt-doped cadmium langbeinite, K2Cd2(SO4)3, the consequences of the doping with regard to site occupancies and low signal strength are discussed, and some details of data modelling are considered. The problem of modelling the spectrum of Finero sapphirine is taken as an example, and it is shown that even simple and evidently inadequate models can provide useful information.

The results of optical spectroscopic investigation of the P213-P212121 transition in K2(Cd0.98Co0.02)2(SO4)3 langbeinite are presented. The trigonal splitting of the spin allowed 4T1g(F)-4T1g(P) transition has been determined, and shows a linear increase with increasing temperature in the high temperature cubic phase, and a constant value in the low temperature phase. This is in good agreement with previous structural work on this material, and it is concluded that optical spectroscopy of doped materials can provide useful information about site distortions.

The sorption properties of iron-modified zeolite (IMZ) and the kinetics of zinc and cadmium uptake by the IMZ were investigated by the batch method. Two kinetic stages were observed, fast uptake up to 240 min, followed by slow uptake up to equilibrium. Kinetic results were fitted to the reaction and diffusion kinetic models, which indicated that intra-particle diffusion was the rate-limiting step. The Vermeulen’s approximation model was used to predict the quantity of Zn and Cd ions removed per gram of IMZ. The results of the successive sorption and desorption of Zn and Cd ions, with different electrolyte solutions, showed the best desorption efficiency with sodium salt solutions. Four successive repetitions of the sorption/desorption cycles showed a small difference between the amount of sorbed and desorbed Zn and Cd ions from the second to the fourth cycle. This indicates excellent sorption/regeneration properties of the IMZ.

An assessment of topsoil (5–20cm) metal/metalloid (hereafter referred to as metal) concentrations across Glasgow and the Clyde Basin reveals that copper, molybdenum, nickel, lead, antimony and zinc show the greatest enrichment in urban versus rural topsoil (elevated 1.7–2.1 times; based on median values). This is a typical indicator suite of urban pollution also found in other cities. Similarly, arsenic, cadmium and lead are elevated 3.2–4.3 times the rural background concentrations in topsoil from the former Leadhills mining area. Moorlands show typical organic-soil geochemical signatures, with significantly lower (P<0.05) concentrations of geogenic elements such as chromium, copper, nickel, molybdenum and zinc, but higher levels of cadmium, lead and selenium than most other land uses due to atmospheric deposition/trapping of these substances in peat. In farmland, 14% of nickel and 7% of zinc in topsoil samples exceed agricultural maximum admissible concentrations, and may be sensitive to sewage-sludge application. Conversely, 5% of copper, 17% of selenium and 96% of pH in farmland topsoil samples are below recommended agricultural production thresholds. Significant proportions of topsoil samples exceed the most precautionary (residential/allotment) human-exposure soil guidelines for chromium (18% urban; 10% rural), lead (76% urban; 45% rural) and vanadium (87% urban; 56% rural). For chromium, this reflects volcanic bedrock and the history of chromite ore processing in the region. However, very few soil types are likely to exceed new chromiumVI-based guidelines. The number of topsoil samples exceeding the guidelines for lead and vanadium highlight the need for further investigations and evidence to improve human soil-exposure risk assessments to better inform land contamination policy and regeneration.

This study was conducted to verify whether vitamin (Vit) E or natural clay as feed additives has the potential to modulate the deleterious effects resulting from exposure to cadmium (Cd) in growing Japanese quail. 648 Japanese quail chicks (1 week old) were used to evaluate the effects of dietary Cd (0, 40, 80 and 120 mg/kg diet) and two levels of Vit E (0, 250 mg/kg diet) or two levels of natural clay (0 and 100 mg/kg diet) to study the influences of Cd, Vit E, clay or their different combinations on growth performance, carcass traits, some blood biochemical components and Cd residues in muscles and liver. Live BW and weight gain of quails were linearly decreased with increasing dietary Cd levels. Moreover, feed conversion was significantly worsened with increasing Cd level. Mortality percentage was linearly increased as dietary Cd level increased up to 120 mg/kg diet. Carcass percentage was linearly decreased as dietary Cd level increased. While, giblets percentage were linearly and quadratically differed as dietary Cd level increased. Cd caused significant changes in total plasma protein, albumin, globulin, A/G ratio, creatinine, urea-N and uric acid concentrations as well as ALT, AST and ALP activities. Increasing dietary Cd level was associated with its increase in the muscles and liver. Dietary supplementation with 250 mg of Vit E/kg diet or 100 mg clay/kg improved live BW, BW gain and feed conversion when compared with the un-supplemented diet. Quails fed diet contained 250 mg Vit E/kg and those fed 100 mg clay/kg had the highest percentages of carcass and dressing than those fed the un-supplemented diet. Blood plasma biochemical components studied were better when birds received 250 mg of Vit E/kg diet and those received 100 mg clay/kg. Cd residues in the muscles and liver were significantly less in the birds had 250 mg of Vit E/kg or those received 100 mg clay/kg diet than those un-supplemented with Vit E. Growth performance traits and blood plasma biochemical components studied were significantly affected linearly by the interactions among Cd and each of Vit E and clay levels. In conclusion, the present results indicate that the deleterious effects induced by Cd plays a role in decreasing the performance of Japanese quail and that dietary supplementation with natural clay or Vit E may be useful in partly alleviating the adverse effects of Cd.

The aim of this study was to investigate the effects of different levels of cadmium supplementation (0, 5, 10, 20, 40 and 80 mg/kg) in the diet on performance, egg quality, tibia biomechanical properties and eggshell and bone mineral contents in laying quails. In this 10-week trial, a total of 96 laying quails, aged 21 weeks, were randomly distributed among six experimental groups. Each experimental group contained four replicates of four birds each. The performance parameters were adversely affected quadratically when cadmium was added to the diets in the concentrations of 20 mg/kg and above (P<0.01). The specific gravity and eggshell weight were maximal with the addition of 20 mg/kg cadmium to the diet. The biomechanical properties of the tibia were negatively affected by cadmium supplementation in quails (P<0.05). The eggshell boron content decreased linearly (P<0.001) with cadmium supplementation to the diet. The cadmium content in bone increased when cadmium was added to the diets (P<0.001). The bone boron concentration decreased as dietary cadmium supplementation was increased (P<0.001).

The in vitro effect of cadmium (Cd) on apical segments of Pterocladiella capillacea was examined. Over a period of 7 days, the segments were cultivated with the combination of different salinities (25, 35, and 45 practical salinity units) and Cd concentrations, ranging from 0.17 to 0.70 ppm. The effects of Cd on growth rates and content of photosynthetic pigments were analyzed. In addition, metabolic profiling was performed, and samples were processed for microscopy. Serious damage to physiological performance and ultrastructure was observed under different combinations of Cd concentrations and salinity values. Elementary infrared spectroscopy revealed toxic effects registered on growth rate, photosynthetic pigments, chloroplast, and mitochondria organization, as well as changes in lipids and carbohydrates. These alterations in physiology and ultrastructure were, however, coupled to activation of such defense mechanisms as cell wall thickness, reduction of photosynthetic harvesting complex, and flavonoid. In conclusion, P. capillacea is especially sensitive to Cd stress when intermediate concentrations of this pollutant are associated with low salinity values. Such conditions resulted in metabolic compromise, reduction of primary productivity, i.e., photosynthesis, and carbohydrate accumulation in the form of starch granules. Taken together, these findings improve our understanding of the potential impact of this metal in the natural environment.