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Determination of hydrogen sulphide in beer by the method of Brenner et al. has been examined. As the copper content of beer, and the time and temperature of storage of copper-containing beer, seem to influence highly the figures obtained, this method can hardly be considered to give reliable results, and may only be applied for beers with low copper contents (less than 0.05 p.p.m.). Though a mechanism reaction between copper and certain sulphur compounds from beer is unknown, it is most probable that the metal gradually forms a complex with sulphur compound(s); this complex after acidification with hydrochloric acid splits off hydrogen sulphide. It is unlikely that methionine, cystine or dimethyl sulphide are among these particular sulphur compounds.

Summary The copper-deficiency condition in cereals known as‘wither-tip’has been found in a limited area in south-east Scotland during the past ten years. This condition has been consistently associated with a low level of total copper in the surface horizon. The distribution of‘wither-tip’and low copper content is directly related to the presence of one soil type, namely Eckford series, within the fields in question. Analysis of IOO surface soils sampled in south-east Scotland suggests that a substantial proportion of the fields in this region are copper deficient or potentially copper deficient.

A preliminary investigation had been made into the evolution of copper tolerance in some Californian populations ofMimulus guttatusgrowing on abandoned copper mines. It has been shown that populations growing on soil with normally toxic levels of copper were tolerant to this heavy metal. There was also some indication of an increase in tolerance to zinc, lead and nickel in the copper tolerant populations, even when the soil was not particularly rich in these other metals. With one exception, populations on non-contaminated soils were non-tolerant as judged by root growth in aqueous solutions or soil containing copper. Furthermore, there was a marked difference in germination and seedling establishment on copper soil between stocks originating from mine and from non-mine environments. The superiority of the mine populations under such circumstances was less marked when established plants were potted up in mine soil. By testing theF1progeny of crosses involving tolerant and non-tolerant parents it was found that copper tolerance is dominant in effect at low copper concentrations, intermediate at intermediate concentrations, and recessive in effect at high copper concentrations. When the plants had been grown on normal soil there appeared to be a requirement for copper at low concentrations among the offspring of tolerant parents. It is suggested that this may result from the mechanism of tolerance by complexing the copper and thus making it unavailable to the plant. The genetic control of zinc and lead tolerance is not clear, but there is evidence that zinc tolerance may be dominant at concentrations of zinc in solution of 15 parts/106.

Ascorbic acid at a concentration of 10 M was a more effective pro‐oxidant in the presence of low copper concentrations than at high concentrations, particularly in the initial stages of oxidation or in the lower pH range (5·5–4·7). This suggested a much more complex role for ascorbic acid than that of copperreducing agent. Reaction of the ascorbic acid radical with oxygen and consequent formation of free HO' radicals was considered to be the most likely initiation reaction resulting from the oxidation of ascorbic acid to dehydroascorbic acid by copper. Dehydroascorbic acid was also found to be an effective pro‐oxidant in the presence of copper.

Extract Raw meat commonly forms the basic diet of weanling dogs. Although there are many reports of the development of bony changes and thyroid enlargement on such diets (see discussion) high mortality has not been reported. In the case described here, all but one of a litter of eight five-month-old German Shepherd pups on a raw meat diet died in the space of two weeks, with enlarged thyroids, bony changes and low liver copper levels.

Neutrophils from cattle with copper deficiency induced by molybdenum (0·052 mmol molybdenum kg−1 diet) or iron (8·95 mmol iron kg−1 diet) had an impaired ability to kill ingested Candida albicans and were less viable than those from copper-supplemented cattle in in vitro tests of function. Restricted intake (80 per cent of ad libitum) of a copper-adequate diet by cattle also decreased neutrophil candidacidal acitivity and viability. Additionally, the ingestion of C albicans by neutrophils was impaired by the molybdenum or iron treatments but not by restricted food intake. The changes in neutrophil function and the severity of copper deficiency, in biochemical terms, induced by the molybdenum or iron treatments were greater than those induced by diets of low copper content.

The mean (+/- sd) liver copper level of 186 red deer (Cervus elaphus) (87 stags and 99 hinds) on the island of Rhum was 51.26 +/- 44.1 ppm dry matter. The level found in the south-east part of the island was significantly higher than elsewhere in hinds, but not in stags. Levels below 20 ppm dry matter, comparable to those found in cases of enzootic ataxia in deer parks, occurred in 18 stags and 20 hinds. Since enzootic ataxia has never been observed on Rhum, it is deduced that low copper status is not of itself the causal factor in that disease. No significant correlation was found between liver copper levels and stocking rate, age, carcase weight, antler weight, antler specific gravity, hind fertility, natural mortality or transferrin phenotype. It is concluded that above a low but perhaps critical level, the copper status of red deer merely reflects the dietary intake of that element.

The teratogenicity of D-penicillamine was studied using the Sprague-Dawley rat. Fetuses from rats fed diets containing 0.83% D-penicillamine during pregnancy had a high incidence of malformations. Maternal and fetal tissue copper levels were significantly lower in the D-penicillamine group than in controls, suggesting that the teratogenicity of the drug may be due in part to the induction of copper deficiency by its chelating properties.

A sensitive, accurate and fast catalytic method is proposed for determination of copper in blood serum, based on a new catalytic reaction—oxidation of 1,3,5-trihydroxybenzene by H2O2. The method permits copper to be determined down to 1 ng/ml in a sample of 0.10 ml of blood serum with a sufficient accuracy and precision even in sera with abnormally low copper assay. Twenty samples can be analysed per hour by a very simple procedure without separation of the metal to be determined.

Zinc and copper concentrations were analysed from cariesfree deciduous teeth of 125 Finnish children, 6-7- and 9-10-year-olds, from three cities. Enamel and dentine were separated and prepared into pills which were analysed individually with the proton induced x-ray emission spectrometry (PIXE) method. The total mean (+/- SD) zinc concentrations for enamel and dentine were 143 +/- 31 and 133 +/- 36 ppm, respectively, and are in agreement with the values reported recently. The median copper concentration for enamel was 0.54 ppm with a range from 0.0 to 4.29 and for dentine 0.27 ppm with a range from 0.0 to 3.60 being among the lowest reported. The low copper values are interesting as to the possible association with the development of atherosclerosis. Geographical differences were noted between the zinc concentrations of the three cities, the children of Helsinki having significantly higher zinc values than the children of Kuopio and Oulu. No linear correlation was found between zinc and copper concentrations at the individual level.

Methods for the control of induced or simple hypocupraemia in cattle were tested using a free-choice copper supplement or by adding a soluble copper salt to the water supply, using a specially designed proportioner. In molybdenum induced hypocupraemia the provision of a free-choice supplement containing 2500 mg Cu per kg resulted in only 10 out of 18 of the cows tested having adequate serum copper levels after a five month grazing period. Supplementation of water supplies to a level of 5 mg Cu per litre was effective in raising and maintaining serum copper at normal levels in a herd of low copper status when offered for a similar period. In experimentally produced molybdenosis, 2 to 3 mg per litre in drinking water corrected the associated diarrhoea and abolished the anomalous blood fractions found at high levels of molybdenum intake in three and five days respectively. It is suggested that water supplementation using a proportioner such as the one described is an effective way of combating both simple and induced hypocupraemia in grazing cattle.

The distribution of hardness was determined in sectioned amalgam restorations prepared with four alloys with different particle shape and copper content, and were condensed into the prepared cavity as in usual clinical practice. The high copper amalgams were apparently harder than the low copper amalgams, the single compositional high copper amalgam being the hardest among them. The hardness of amalgam adjacent to the lateral cavity wall was obviously smaller than that of the center, and the low copper lathe-cut amalgam had an extremely small hardness. The top of the restoration had a remarkably smaller hardness which was especially apparent with single compositional high copper amalgam. Therefore, the hardness at the margin of an restoration was not the same as that of the center but in considerably smaller, regardless of the alloy type used. Accordingly, the mechanical properties of the marginal region of a high copper amalgam restoration is considered not as favorable as expected from the result of commonly used mechanical tests, compared with low copper amalgams.

The kinetics of serosal copper transfer and the distribution of copper between metallothionein (MT) and a high-molecular-weight protein fraction (HMWPF) within the mucosal cells were examined, using isolated duodenal segments from rats fed different amounts of zinc. No difference in the Vmax or Km for serosal transfer could be detected between the different zinc groups, suggesting that zinc did not affect this aspect of copper absorption. When intestinal segments from rats fed the low zinc diet were incubated in high copper media, the majority of the copper was associated with the HMWPF, while those from rats fed the high zinc diet had the largest proportion bound to MT. All the intestines incubated in the low copper media, regardless of rat zinc status, had the majority of copper associated with MT. These results suggested that with the low zinc diet, the limited amount of MT present was saturated, and the excess copper was bound to the HMWPF. With larger intakes of zinc, MT synthesis was induced, and the larger amount of this protein was not as readily saturated, resulting in less copper binding to the HMWPF and more to MT. It is suggested that zinc interferes with copper absorption by inducing MT, which sequesters copper in the mucosal cells, making it unavailable for serosal transfer. The copper bound to the HMWPF is available for transfer.

In the literature there is controversy over the existence of a correlation between creep and marginal deterioration of amalgam restorations. It was the aim of this study to re-investigate this correlation. In five clinical trials, 2068 amalgam restorations were made of six conventional alloys and ten high copper systems. The results show a correlation between creep and marginal fracture in the conventional, low copper amalgams. No correlation could be found for the group of high copper, non-gamma-2, amalgams. It is emphasized that dental practitioners should not buy their amalgam alloy on the basis of creep data, because wrong decisions might be taken. Evidence from a controlled clinical study is a more reliable criterion.

The reaction of indoles with copper(II) chloride has been studied in acetonitrile. At low copper(II):indole ratios, dimers are formed in the presence of dioxygen, oxygenated products are obtained, and at large copper(II) :indole ratios, pyrrole ring-chlorinated products are formed in yields of up to 92 %. The reactions are postulated to proceed via the radical cations of the indoles formed in an electron-transfer reaction.

The copper content of and radiocopper uptake in fibroblast cultures were studied to evaluate their usefulness for the diagnosis of Wilson's disease. We used methods closely related to those described in the literature, and applied these to cell lines of six patients with Wilson's disease and 12 controls. The results were: (1) The copper content of the cytosol of skin fibroblasts derived from patients with Wilson's disease was lower than that of controls when the cells were grown in a medium with a low copper concentration (0.7 mumolL-1); increased copper concentration (157 mumol L-1 in the medium failed to demonstrate any difference between normal fibroblasts and those derived from patients with Wilson's disease. (2) Radiocopper uptake studies did not differentiate between normal fibroblasts and fibroblasts from patients with Wilson's disease. We conclude that the cytosolic copper content of fibroblasts grown in a low copper medium is a potential diagnostic tool in Wilson's disease. At present not all controls can be distinguished from the Wilson cells; ways must be sought, therefore, of improving the technique.

Crossed immunoelectrophoresis of human serum revealed two heterogeneity types of ceruloplasmin with different electrophoretic migration. The two types both consisted of peptides with Mr 150,000, 100,000 and 45,000, which were interpreted as native ceruloplasmin and two hydrolytic fragments. The two types were different in copper content, and one type could reversibly be changed into the other. The glycan microheterogeneity of ceruloplasmin was analyzed by crossed affinoimmunoelectrophoresis with free Lens culinaris agglutinin (LCA) and wheat germ agglutinin (WGA). A third of the ceruloplasmin molecules, both high and low copper type, bound to LCA and two thirds to WGA. The heterogeneity and the microheterogeneity of ceruloplasmin in two groups of patient sera were compared to sera from healthy individuals. The ceruloplasmin type with respect to copper content was a much better factor than either glycan microheterogeneity or total serum concentration in discriminating between the three groups.

The fracture toughness (KIC) has been measured (at 1 week) for a selection of sixteen amalgam products. This included low copper (i.e. Cu less than 6%) and high copper (both single component and admixed) products in milled and spherical powder forms. The results have shown that the fracture toughness decreases progressively as the copper content increases. The admixed high copper products possess superior fracture toughness to those containing a single component powder. These results have been attributed to differences in the microstructures produced by changes in composition and form in which the copper addition is made.

A conventional low copper amalgam was placed in cavities with and without smear layer removal and the amalgam restorations were covered with a resin overlay. The restored teeth were retrieved at 2, 28 and 56 days postoperatively in order to test for leakage and then pulpal reactions. More inflammation was seen in the teeth from which the smear layer had been removed. Abscesses were present in 6 teeth at 28 days but only one was associated with demonstrable bacteria. This study does not support smear layer removal before insertion of low copper amalgam restorations.

Effects of mixing time on the microstructure of several low and high copper amalgams were observed. An apparent relationship was found between the microstructure, especially enclosed porosities, and physical properties reported previously1). In regard to the mixing time, a greater influence was observed with either lathe-cut or high copper than spherical or low copper, with respect to the particle shape and copper content of the alloys. Sufficient mixing is required for lathe-cut high copper alloys.However, differences in the mixing characteristics were often observed even with alloys having similar particle shape or composition. This may be due to the dissimilar surface characteristics of alloy particles, causing the differences in affinity with mercury. Prolonged mixing to eliminate the porosities in the set amalgam may cause the poor results, such as remarkably shortened working time and increase in shrinkage during setting.The mixing time of an amalgam alloy should be estimated on both technological and practical bases.

A nephropathy was observed in ewes and lambs fed a semi-purified diet of low copper content. With a few exceptions, the severity of the renal lesions varied with the length of time the diet was fed and ranged from glomerular basement membrane thickening and hypercellularity to glomerular and tubular atrophy, degeneration and mineralization; in moderate and severely affected cases, arteriosclerosis was also a feature. The possible role of partial renal ischaemia in the pathogenesis of the lesion is discussed.

The content and rationale of Standards for Dental Amalgam Alloys are discussed. The properties of amalgams made from 50 alloys used in Australia were determined according to methods in the Standards and the results are presented to enable comparison between low and high copper amalgams. The limits for the physical tests are discussed in the light of the range of values obtained. In general, the high copper amalgams showed higher one hour compressive strengths, lower creep and plastic deformation than low copper amalgams. No difference in dimensional change was found.

A patient with progressive neurological disease resembling Wilson's disease but in whom Kayser-Fleischer rings were absent, was given 67Cu and 64Cu, orally and intravenously, to measure the rate of absorption of copper using a convolution integral. The data show an abnormal distribution of body copper resulting in low copper concentrations in plasma, urine and liver but with an accumulation in the lower bowel probably due to a defect in mucosal transport. The importance of differentiating this condition from Wilson's disease is stressed.

This study was devoted to examining the application of copper dodecanoate as a non-contaminant antifouling pigment due to its low copper content and fatty acid nature. For this purpose, antifouling paints with mono-component epoxy resin and rosin matrixes were formulated, and their antifouling efficiency was evaluated. Before its incorporation into the different formulations, the synthesized pigment was characterized. Immersion tests in a marine environment were carried out for 12 months to evaluate the antifouling efficiency of the developed paints; the results were compared with those from a commercial paint. The antifouling efficiency of the new epoxy formulation was found to be considerably higher than that of the rosin formulation and very similar to that of the commercial paint. Most importantly, the release of copper from the epoxy paint formulated with copper dodecanoate was 73.5% lower than that of the commercial paint, suggesting prolonged activity of the developed paint.

Tule elk (Cervus eiirphus uuuuos serum, x’ 2 1.4 ppm). These levels were consistent with documented coppsr defi- ciency in wild and domestfe ruminants. Copper serum levels increased in response to copper enriched dietary supplements and declined after the elk stopped eating the supplements. Analysis of plant and soil samples showed both are deficient in copper and normal in molybdenum and sulfur-sulfatss. Deficiency in plants and sops at Point Reyes are probably due to low copper levels in the underlyitq granitic parent material. Key Words: Corvus ebhus tumuodes, copper, molybdenum and sulfur levels in elk, vegetation and sops

Top of pageAbstract The Brindled mouse mutant is a model for the Kinky Hair syndrome. Male Brindled hemizygous suckling mice demonstrate poor growth and neurologic deterioration beginning during the first week of life and ending with death by the end of the second week. Newborn Brindled carriers are asymptomatic with normal brain copper concentration; liver copper concentration is low and the renal copper is high. Newborn carrier pups suckled by Brindled dams put on low copper diets on the day of parturition, however, show deficient weight gain by the age of 6 days and by 12 days weigh approximately one-half their normal litter-mates. Neurologic symptoms developed in the copper-deficient young carriers by age 12-14 days while their normal litter-mates remained asymptomatic. Tissue copper studies demonstrate that the liver and brain copper concentration in the carrier is no different from that of the normals, although the renal copper is greater than twice as high. On copper-deficient diets, the brain and liver concentrations of normal and heterozygous young decrease to comparable levels, but heterozygotes also develop systemic and neurologic symptoms. These observations are thought to implicate an abnormality in copper utilization in Brindled carriers brought out by marginal copper intake.

The ratios of ( trace- ) minerals may be of importance for their retention from human milk (HM) and formula. We determined the Ca, Cu, Fe, K, Mg, Mn, Na, P and Zn concentrations in more than 2300 samples of HM of 10 healthy mothers collected 2,5,8,12,16 weeks post partum. Zn/(trace-) mineral ratios (median and range) are compared with an unsupplemented formula (Pre-Aptamil (PA); Zn = 1.26 mg/l). The high Zn/Cu ratio in PA may partly be ascribed to the low copper concentration (0.12 mg/l), whereas high manganese levels leading to low Zn/Mn ratios are found in formulas without supplementation. Zn supplementation to values about twofold the present level (2-3 mg/l) would render an improved approach to ratios found in HM for Ca, Fe, Mg, Mn, Na. The results are of particular concern in view of isolated supplementation of e.g. iron, which might lead to inverse ratios as found in human milk.

THE striking increase in the copper concentration of the human liver, which begins during fœtal life and reaches its maximum at birth, has not yet been satisfactorily explained. Since the importance of copper as a catalyst for haemoglobin formation is now conclusively proved for many higher animals, most authors consider the ‘congenital copper deposit’, too, to be connected with this function. Two hypotheses have been suggested in this respect: (a) copper is accumulated in the fœtal liver, because this is the chief site of blood formation during embryonic life; (b) copper is stored in the fœtal liver to compensate for the low copper content of milk during lactation, just as in the case of iron.

THE occurrence of a suspected copper deficiency in cattle in Aberdeenshire was recently reported1, the evidence being based on the low copper content of the pastures and on the similarity of the symptoms to those of ‘peat scours’ in New Zealand described by Cunningham2. No blood copper data were given to correlate the suspected low copper status of the cattle with the low copper value of the pasture.

Kinky-hair syndrome, a progressive neurodegenerative disorder which affects infant males and is characterized by unusual hair, seizures, psychomotor retardation, growth failure, and early death, was first described by Menkes et al. 1 Since the original description, 11 more cases have been reported from this country. 2 Additional features, including bone changes and tortuous cerebral vessels, have been noted subsequently. Recently Danks et al, 3 from Australia, have reported very low levels of copper and copper oxidase in the blood in five cases. Poor absorption of copper was thought to be the mechanism involved, although this was not proven. This paper presents a new case of kinky-hair syndrome showing typical clinical and radiological features and very low copper levels in the blood, urine, and hair. Relevant literature in relation to copper deficiency in man and animals is reviewed.