Standardization of Sandwich-Structured Cu-Glass Substrates Embedded in a Flexible Diode Laser-Plasma Interface for the Detection of Cholesterol.

This study introduced sandwich-structured copper-glass substrates for standardization of laser desorption and plasma ionization. For standardized quantitative analysis, cavities were constructed which allow better reproducibility in droplet deposition and for laser application. Applying the diode laser, molten substrate material is incorporated into the glass, being trapped inside. Therefore, this method can be separated from laser ablation, achieving high ion signals without ablating material from the surface. Flexible microtube plasma (FµTP) was selected as the ionization source, this being the first time that laser desorption and FµTP ionization are coupled. This laser-plasma interface was applied to the detection of cholesterol, which showed a significantly improved limit of detection of 0.46 ng and linear dynamic range of 3 orders of magnitude in positive ion mode compared to other (ambient air mass spectrometry) methods. The main reason was the change of phase on the copper surface. The dehydrated molecule [M-H2O+H]+ was the base peak of the spectrum and no further dissociation or fragmentation was observed. Blood plasma was spiked with cholesterol. In a 1:100 chloroform dilution, the presence of the plasma was neglectable and led to the same detection limits and linear dynamic range as in the cholesterol standard. No sample preparation or internal standards were needed for calibration. The physical effects of the surface modification were investigated, including the calculation of the laser beam waist to simplify the comparison and reproducibility of results.

A new anion exchange purification method for Cu stable isotopes in blood samples.

The isotopic composition of iron, zinc, copper, and cadmium (δ56Fe, δ66Zn, δ65Cu, and δ114Cd) are novel and promising tools to study the metabolism and homeostasis of trace metals in the human body. Serum δ65Cu has been proposed as a potential tool for diagnosis of cancer in liquid biopsy, and other metals may have similar utility. However, accurate analysis of trace metal isotopes is challenging because of the difficulties in purifying the metals from biological samples. Here we developed a simple and rapid method for sequential purification of Cu, Fe, Zn, and Cd from a single blood plasma sample. By using a combination of 11 M acetic acid and 4 M HCl in the first steps of column chemistry on AG-MP1 resin, we dramatically improve the separation of Cu from matrix elements compared to previous methods which use concentrated HCl alone. Our new method achieves full recovery of Cu, Fe, Zn, and Cd to prevent column-induced isotope fractionation effects, and effectively separates analytes from the matrix in order to reduce polyatomic interferences during isotope analysis. Our methods were verified by the analysis of isotope standards, a whole blood reference material, and a preliminary sample set including five plasma samples from healthy individuals and five plasma samples from cancer patients. This new method simplifies preparation of blood samples for metal isotope analysis, accelerating multi-isotope approaches to medical studies and contributing to our understanding of the cycling of Fe, Zn, Cu, and Cd in the human body. Graphical abstract ᅟ.

Evaluation of current copper bioavailability tools for soft freshwaters in Sweden.

The Water Framework Directive (WFD) in Europe calls for an improved aquatic ecological status. Biotic ligand models (BLM) have been suggested as a possible tool assisting in the regulatory process. The aim of this study was therefore to investigate the applicability of BLM under the WFD to set environmental quality standards (EQS), in particular regarding copper in Swedish freshwaters of which many are softer than those used for model calibration. Three different BLMs, one acute and two chronic, were applied to water chemistry data from 926 lakes and 51 rivers (1530 data entries) and evaluated with respect to their calibration range for input parameters. In addition, the predicted no-effect concentration (PNEC) for copper was calculated. From the 1530 data entries, 750 ended up outside of the BLM calibration range, when looking at the chemical parameters Ca(2+), alkalinity, pH and DOC, primarily due to low carbonate alkalinity. Furthermore, the calculated Cu PNECs were higher than the suggested Swedish limit for Cu (4µgL(-1)) in surface waters for 98% and 99% of the cases concerning lakes and rivers, respectively. To conclude, our findings show that water chemical characteristics outside of the calibration ranges are quite common in Sweden and that the investigated models differ in how they calculate toxicity concerning Cu under these conditions. As a consequence, additional work is required to validate the BLMs by use of bioassays with representative species of soft waters. Such results will show if these models can be used outside of their calibration ranges and also which of the models that gives the most reliable results.

Defining reference values of trace elements in the tear film: diagnostic methods and possible applications.

The study has been performed on tears of apparently healthy subjects who live and work in urban and rural areas, respectively. After the collection the following elements were investigated: chromium (Cr); arsenic (As); copper (Cu); zinc (Zn); selenium (Se); rubidium (Rb); barium (Ba); lead (Pb) and cobalt (Co). Significantly higher values of As were found in subjects living and working in rural areas as compared to those found in urban area residents (0.290 vs. 0.025; p<0.001). Conversely, Ba and Pb were significantly lower in rural area residents (1.10 vs. 2.50, p=0.027 and 1.70 vs. 1.10, p=0.057, respectively). Our data show that trace elements analysis in tears is possible; further studies could define if it could be a reliable biomarker in persons exposed to high concentration of trace elements due to working or environmental reasons.

Copper and zinc water quality standards under the EU Water Framework Directive: the use of a tiered approach to estimate the levels of failure.

Environmental quality standards are an important tool for assessing the chemical quality of water bodies under the Water Framework Directive. However, there must be confidence in assessments of any failure to avoid disproportionate investment in unnecessary risk reduction. Metals present a number of unique challenges for environmental regulators in that they are naturally occurring and their ecotoxicology is driven, in part, by the physico-chemical conditions of the water body in which they are present. This paper describes the use of a tiered approach that could be adopted to assess compliance with any future environmental quality standards for metals under the Water Framework Directive. Through this approach, the use of background concentrations is considered and also bioavailability via the use of biotic ligand models. This assessment is based on an analysis of routine Environment Agency chemical monitoring data combined with biological indices to support results of the approach. Using copper and zinc as examples, it is shown that it is important to take account of background concentrations and the bioavailability of metals, otherwise the risk of impact from metals may be significantly overestimated. The approach presented here provides a methodology by which regulators and the regulated community may implement surface water standards for metals under the Water Framework Directive.

Simultaneous determination of nickel and copper by H-point standard addition method-first-order derivative spectrophotometry in plant samples after separation and preconcentration on modified natural clinoptilolite as a new sorbent.

For the simultaneous determination of nickel(ll) and copper(ll) in plant samples, a rapid and accurate method was developed. In this method, solid-phase extraction (SPE) and first-order derivative spectrophotometry (FDS) are combined, and the result is coupled with the H-point standard addition method (HPSAM). Compared with normal spectrophotometry, derivative spectrophotometry offers the advantages of increased selectivity and sensitivity. As there is no need for carrying out any pretreatment of the sample, the spectrophotometry method is easy, but because of a high detection limit, it is not so practical. In order to decrease the detection limit, it is suggested to combine spectrophotometry with a preconcentration method such as SPE. In the present work, after separation and preconcentration of Ni(ll) and Cu(ll) on modified clinoptilolite zeolite that is loaded with 2-[1-(2-hydroxy-5-sulforphenyl)-3-phenyl-5-formaza-no]-benzoic acid monosodium salt (zincon) as a selective chromogenic reagent, FDS-HPSAM, which is a simple and selective spectrophotometric method, has been applied for simultaneous determination of these ions. With optimum conditions, the detection limit in original solutions is 0.7 and 0.5 ng/mL, respectively, for nickel and copper. The linear concentration ranges in the proposed method for nickel and copper ions in original solutions are 1.1 to 3.0 x 10(3) and 0.9 to 2.0 x 10(3) ng/mL, respectively. The recommended procedure is applied to successful determination of Cu(ll) and Ni(ll) in standard and real samples.

An inductively coupled plasma mass spectrometry method for relative free copper determination and generation of a paediatric reference interval.

Background Diagnosis of Wilson's disease is currently performed using caeruloplasmin as a first-line screening test; however, this test has well-described limitations. Monitoring of known Wilson's disease patients often uses 24-h urine collection; however, this is inaccurate in children. Methods for directly measuring plasma free copper have been described, but no reference interval data exist for a paediatric population. Methods An inductively coupled plasma mass spectrometry method for measuring free copper was developed and validated, using ultracentrifugation. A paediatric reference interval was generated using 85 plasma samples from children attending outpatient clinics at University Hospital Southampton. Results Results showed no significant contamination of copper using the ultracentrifugation technique, and validation showed the method was accurate and precise with an analytical coefficient of variation between 5 and 7% depending on the concentration of free copper. Conclusions We describe the use and validation of an ultrafiltration inductively coupled plasma mass spectrometry method for plasma free copper with the first published paediatric reference interval. Free copper could provide much needed assistance for the monitoring of Wilson's disease in children and also for adults.

Water-effect ratio of copper and its application on setting site-specific water quality criteria for protecting marine ecosystems of Hong Kong.

Generic water quality criteria (WQC) of a chemical are usually set based on results generated from toxicity tests which were conducted using standard laboratory water with well-controlled physiochemical properties. However, in natural aquatic environments, physiochemical characteristics, such as salinity, total suspended solid, total organic carbon and the co-existence of chemical contaminants, often vary spatially and temporally. These parameters can, in turn, alter the bioavailability of target chemicals and, thus, influence their toxicity to marine organisms. To account for site specificity, the US Environmental Protection Agency's water-effect ratio (WER = site water-LC50 / laboratory water-LC50) procedure can be applied to derive site-specific WQC. Most past studies, however, were conducted for freshwater systems. Here, for the first time, the WER of copper (Cu) was determined for three marine water control zones (WCZs) in Hong Kong: Victoria Harbour, Deep Bay and Southern WCZs. Samples of water were collected from three locations within each WCZ, while acute toxicities to the marine diatom Skeletonema costatum, intertidal copepod Tigriopus japonicus and larvae of marine medaka Oryzias melastigma were determined in site or laboratory (artificial seawater) waters. Results of this study showed that conservative final WER relative coefficients for Cu ranged from 0.57 to 0.73 for the three WCZs, and water from some locations caused >30% mortality in the fish larvae in the controls (without Cu addition). These results suggested that current generic WQC for Cu are likely under-protective for marine organisms in the three areas, and it should be tightened by multiplying it with site-specific WER to offer better protection to marine biodiversity and integrity of the ecosystem.

An evaluation of freshwater mussel toxicity data in the derivation of water quality guidance and standards for copper.

The state of Oklahoma has designated several areas as freshwater mussel sanctuaries in an attempt to provide freshwater mussel species a degree of protection and to facilitate their reproduction. We evaluated the protection afforded freshwater mussels by the U.S. Environmental Protection Agency (U.S. EPA) hardness-based 1996 ambient copper water quality criteria, the 2007 U.S. EPA water quality criteria based on the biotic ligand model and the 2005 state of Oklahoma copper water quality standards. Both the criterion maximum concentration and criterion continuous concentration were evaluated. Published acute and chronic copper toxicity data that met American Society for Testing and Materials guidance for test acceptability were obtained for exposures conducted with glochidia or juvenile freshwater mussels. We tabulated toxicity data for glochidia and juveniles to calculate 20 species mean acute values for freshwater mussels. Generally, freshwater mussel species mean acute values were similar to those of the more sensitive species included in the U.S. EPA water quality derivation database. When added to the database of genus mean acute values used in deriving 1996 copper water quality criteria, 14 freshwater mussel genus mean acute values included 10 of the lowest 15 genus mean acute values, with three mussel species having the lowest values. Chronic exposure and sublethal effects freshwater mussel data available for four species and acute to chronic ratios were used to evaluate the criterion continuous concentration. On the basis of the freshwater mussel toxicity data used in this assessment, the hardness-based 1996 U.S. EPA water quality criteria, the 2005 Oklahoma water quality standards, and the 2007 U.S. EPA water quality criteria based on the biotic ligand model might need to be revised to afford protection to freshwater mussels.

Artificial Leaks in Container Closure Integrity Testing: Nonlinear Finite Element Simulation of Aperture Size Originated by a Copper Wire Sandwiched between the Stopper and the Glass Vial.

Container closure integrity (CCI) testing is required by different regulatory authorities in order to provide assurance of tightness of the container closure system against possible contamination, for example, by microorganisms. Microbial ingress CCI testing is performed by incubation of the container closure system with microorganisms under specified testing conditions. Physical CCI uses surrogate endpoints, such as coloration by dye solution ingress or gas flow (helium leakage testing). In order to correlate microbial CCI and physical CCI test methods and to evaluate the methods' capability to detect a given leak, artificial leaks are being introduced into the container closure system in a variety of different ways. In our study, artificial leaks were generated using inserted copper wires between the glass vial opening and rubber stopper. However, the insertion of copper wires introduces leaks of unknown size and shape. With nonlinear finite element simulations, the aperture size between the rubber stopper and the glass vial was calculated, depending on wire diameter and capping force. The dependency of the aperture size on the copper wire diameter was quadratic. With the data obtained, we were able to calculate the leak size and model leak shape. Our results suggest that the size as well as the shape of the artificial leaks should be taken into account when evaluating critical leak sizes, as flow rate does not, independently, correlate to hole size. Capping force also affected leak size. An increase in the capping force from 30 to 70 N resulted in a reduction of the aperture (leak size) by approximately 50% for all wire diameters. From 30 to 50 N, the reduction was approximately 33%. LAY ABSTRACT: Container closure integrity (CCI) testing is required by different regulatory authorities in order to provide assurance of tightness of the container closure system against contamination, for example, by microorganisms. Microbial ingress CCI testing is performed by incubation of the container closure system with microorganisms under specified testing conditions. Physical CCI uses surrogate endpoints, such as coloration by dye solution ingress or gas flow. In order to correlate microbial ingress CCI and physical CCI test methods and to evaluate the methods' capability to detect a given leak, artificially created defects (artificial leaks) are being introduced into the container closure system in a variety of different ways. In our study, artificial leaks were generated using inserted copper wires between the glass vial opening and rubber stopper. Up to date, the insertion of copper wires introduced leaks of unknown size and shape. With nonlinear finite element simulations, the effective aperture size between the rubber stopper and the glass vial was calculated, depending on wire diameter and capping force, and the leak shape was modelled. Our results suggest that the size as well as the shape of the artificial leaks should be taken into account when evaluating critical leak sizes, as flow rate does not, independently, correlate to the hole size.

Efficacy of a copper-lysine complex as a growth promotant for weanling pigs.

Eight 28- or 35-d experiments involving, 1,301 crossbred pigs weaned at 30 +/- 2 d of age (7.0 to 7.9 kg initial weight) were conducted to evaluate the efficacy of a Cu-lysine complex (CuLys; CuPLEX 80 in Exp. 1 to 5, and CuPLEX 100 in Exp. 6 to 8) at dietary concentrations of 50, 100, or 200 ppm as a growth promoter for weanling pigs. CuPLEX 80 contained 50% Cu in the complexed from (1 mol Cu:2 mol lysine) and 50% Cu as CuSO4.5H2O (CuSO4). All the Cu in CuPLEX 100 was in the complexed form. In general, the addition of Cu from CuSO4 or either CuLys source improved pig performance. Overall, averaged across Cu sources, there were no differences between 100 and 200 ppm of Cu in the magnitude of improvement over controls for daily gain (14.0 vs 14.3%), daily feed (12.1 vs 10.7%), or feed:gain ratio (1.6 vs 3.0%). Averaged across levels of Cu supplementation, the percentage improvements from CuLys additions were greater than those for CuSO4 for growth rate (16.8 vs 11.5%; P < .03) and feed intake (14.1 vs 8.7%' P < .01), but not for efficiency of feed utilization (2.2 vs 2.4%). These trends were similar for both sources of CuLys. Liver Cu concentrations of pigs receiving 200 ppm of Cu in the totally complexed form (CuPLEX-100) were lower (P < .025) than concentrations in those receiving 200 ppm of Cu from CuSO4 (111 vs 221 ppm).(ABSTRACT TRUNCATED AT 250 WORDS)

Evaluation of copper sulfate and a copper lysine complex as growth promoters for weanling swine.

Two 5-wk trials using 176 weanling pigs (average initial weight of 8.3 kg and age of 31 d) were conducted to examine the effect of feeding varying levels of dietary Cu from copper sulfate (CuSO4) or a copper lysine complex (CuLys) on performance, mineral stores, serum copper, and serum mitogenic activity. Dietary treatments were 0 (15 mg/kg of Cu in basal diet), 100, 150, or 200 mg/kg of supplemental Cu from CuSO4 or CuLys. Average daily gain and ADFI increased linearly (P < .01) with increasing dietary levels of Cu during wk 1 to 2, 3 to 5, and 1 to 5, with no difference (P > .10) between the Cu sources. Overall gain:feed ratios were not consistently affected by Cu source. Dietary Cu linearly increased liver, kidney (P < .001), and brain (P < .05) concentrations of Cu. In the liver, the linear response to supplemental Cu differed between Cu sources (P < .001); pigs fed 200 mg/kg of Cu from CuLys had the highest concentration of Cu. Serum Cu concentrations increased linearly during wk 1 to 2 (P < .01), 3 to 5, and 1 to 5 (P < .001), with no difference (P > .10) between sources. Serum mitogenic activity increased linearly during wk 1 to 2 and 1 to 5 (P < .05). Growth performance was linearly improved as the dietary level of Cu increased from 15 to 200 mg/kg, with similar responses for both Cu sources. Serum and tissue concentrations of Cu were generally equally affected by the two Cu sources, except liver Cu concentration, which was onefold higher for pigs fed 200 mg/kg of Cu as CuLys.

Cements for permanent luting: a summarizing review.

Three cement systems are favored for permanent luting of cast restorations. These include zinc phosphate, reinforced zinc oxide-eugenol, and polycarboxylate cements. Although others have been used in the past and new luting media are anticipated for the future, the status of currently used cement for luting is based mainly on the results of laboratory research and on clinical experience. Zinc phosphate cement, with an impressive 100-year history, currently holds the advantage. Future comprehensive clinical studies, correlated with results of physical and biological testing, may eventually direct the clinican's preference to another, newer material. It is hoped that properties and strength values that are clinically significant also will be identified, so that laboratory tests can be more predictive of clinical success.

Efficacy of a novel copper-based footbath preparation for the treatment of ovine footrot during the spread period.

OBJECTIVE: To determine the efficacy of a novel copper based footbath preparation (CHF-1020) for treatment of ovine footrot during the spread period. DESIGN: A series of field trials with treated and control groups run together. ANIMALS: Mobs of at least 125 sheep on each of six properties in southern New South Wales with equal numbers of controls. PROCEDURE: Sheep of group A were treated after minimal paring by making them stand in CHF-1020 for 15 minutes. Treatment was undertaken at intervals throughout the period of the trials (14 September to 17 December 1993). Group A sheep were run on the same pasture as those from group B (untreated sheep). RESULTS: The percentage of sheep exhibiting clinical signs of ovine footrot at the start of the trial ranged from 35 to 88% at score 3 or higher, using a 0 to 5 footscoring system. During the trial, the percentage of infected sheep (greater or equal to score 2) in group B increased and ranged from 40 to 90%. The level of infected sheep in group A on each property was reduced progressively to 1 to 16%. Cure rates of 45 to 94% were achieved, with the lowest rate being on a property with a metal footbath. The next lowest cure rate was 73%. Results indicated that treatment should be undertaken at 2-weekly intervals while spread continues. Treated sheep can be returned to contaminated pastures. CONCLUSION: CHF-1020 is effective during the spread period and can be used for the progressive eradication of ovine footrot.

[Value of the studies of multimodal evoked potentials for evaluation of neurotoxic effects of combined exposure to lead, copper and zinc]. / Wartosc badan multimodalnych potencjalów wywolanych dla oceny neurotoksycznego wplywu mieszanego narazenia na olów, miedz i cynk.

Central nervous system dysfunction was studied in workers with occupational exposure to Pb+Cu+Zn by measuring somatosensory evoked potentials of short and long latency, visual evoked potentials and brain-stem evoked auditory potentials. The tests were done in 40 workers with a history of exposure from 6 to 19 (mean 14.3) years in a copper foundry. Pb poisoning was not diagnosed in them, but 18 workers had some abnormalities of heme synthesis. Pb concentration in blood was from 11.4 to 62.8 (mean 35.7) mcg% in the whole group. Pb concentration in air in the foundry exceeded 1.1-175 times the MAC value, the concentration of CU exceeded it 7.25 times. Zn concentration was half the MAC value. No significant abnormalities were found in the parameters of multimodal evoked potentials. The obtained data suggest a protective effect of copper and zinc on heme , Pb blood level and conduction velocity of somatosensory, visual and auditory impulses in workers exposed to high Pb air concentration.

[Nutritive value of daily food rations reproduced in different regions of the country. IV. Copper, zinc and manganese levels]. / Wartosc odzywcza calodziennych racji pokarmowych odtwarzanych w kilku regionach kraju. CZ. IV. Zawatosc miedzi, cynku, manganu.

The content of copper, zinc and manganese in daily diets reconstructed in the laboratory in 1988 on the basis of data on the yearly food consumption in 1986 of two social groups (manual and mental workers) with medium income was determined. The diets were prepared for four regions of the country (Warszawa, Lublin, Poznan, Wroclaw). It was found out that the content of copper and zinc in the diets in 1986 and the realisation of recommended dietary allowances for these minerals were lower than in 1973, 1980 and 1981. The degree of realization of the recommended intake of zinc and copper in diets from 1986 was on average 67% and 45% respectively. The content of manganese in the diets was in the range of recommendation. The content of microminerals in the diets was usually similar in the all studied regions of the country.

[Changes in biological activity of turf-podzolic soil of different mechanical composition contaminated with heavy metals]. / Izmenenie biologicheskoi aktivnosti dernovo-podzolistoi pochvy razlichnogo mekhanicheskogo sostava pri zagriaznenii tiazhelymi metallami.

It has been shown that soil pollution with heavy metals (copper, nickel) lead to negative changes in parameters characterizing potential biological activity of soil (nitrogen-fixation, breath, invertase activity, bacteria and fungi count). More profound changes were observed in sandy soil compared to loamy soil. A direct relationship of these effects with the content of mobile forms of heavy metals in soil has been established. For the comparative and prognostic investigation of the danger of soil pollution with heavy metals it has been suggested to use a coefficient of differences in the content of mobile forms and a coefficient of biological effect.

Incorporating bioavailability into management limits for copper in sediments contaminated by antifouling paint used in aquaculture.

Although now well embedded within many risk-based sediment quality guideline (SQG) frameworks, contaminant bioavailability is still often overlooked in assessment and management of contaminated sediments. To optimise management limits for metal contaminated sediments, we assess the appropriateness of a range methods for modifying SQGs based on bioavailability considerations. The impairment of reproduction of the amphipod, Melita plumulosa, and harpacticoid copepod, Nitocra spinipes, was assessed for sediments contaminated with copper from antifouling paint, located below aquaculture cages. The measurement of dilute acid-extractable copper (AE-Cu) was found to provide the most useful means for monitoring the risks posed by sediment copper and setting management limits. Acid-volatile sulfide was found to be ineffective as a SQG-modifying factor as these organisms live mostly at the more oxidised sediment water interface. SQGs normalised to %-silt/organic carbon were effective, but the benefits gained were too small to justify this approach. The effectiveness of SQGs based on AE-Cu was attributed to a small portion of the total copper being present in potentially bioavailable forms (typically<10% of the total). Much of the non-bioavailable form of copper was likely present as paint flakes in the form of copper (I) oxide, the active ingredient of the antifoulant formulation. While the concentrations of paint-associated copper are very high in some sediments, as the transformation of this form of copper to AE-Cu appears slow, monitoring and management limits should assess the more bioavailable AE-Cu forms, and further efforts be made to limit the release of paint particles into the environment.

Development of a certified reference material (NMIJ CRM 7531-a) for the determination of trace cadmium and other elements in brown rice flour.

A certified reference material (CRM) for trace cadmium and other elements in brown rice flour was developed at the National Metrology Institute of Japan (NMIJ). The CRM was provided as a dry powder after drying and frozen pulverization of fresh brown rice obtained from a Japanese domestic market. Characterization of the property value for each element was carried out exclusively by NMIJ with at least two independent analytical methods, including inductively coupled plasma mass spectrometry (ICP-MS), ICP high-resolution mass spectrometry, isotope-dilution ICP-MS, ICP optical emission spectrometry, and graphite-furnace atomic-absorption spectrometry. Property values were provided for six elements (Mn, Fe, Cu, Zn, As, and Cd). The concentration range of the property values was from 0.280 mg kg(-1) of As to 31.8 mg kg(-1) of Zn. The combined relative standard uncertainties of the property values were estimated by considering the uncertainties of the homogeneity, characterization, difference among analytical methods, dry-mass correction factor, and calibration standard. The range of the relative combined standard uncertainties was from 1.1% of Zn to 1.6% of As.