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Characterisation of sewage sludge metals for classification purposes using the potentially leachable metal fraction.

The South African sludge guidelines were revised in 1997 with considerable amendments to the heavy metal loading and usage restrictions. The industry continued using the aqua regia extraction method to characterise and classify sewage sludge. This meant that a Class D sludge (most stable class and sellable product) could not be generated at any South African plant. This caused the industry to seek alternative nonbeneficial disposal methods. It was then realised that the metal limits were in fact the TCLP (Toxicity Characteristic Leaching Procedure) extractable limit. This method was developed to determine the potential of a waste to contaminate ground and/or surface water. The agriculturists, however, use the NH4EDTA extractable fraction to establish metal concentration in soils. This paper specifically aims to establish the feasibility of using the available metals extraction methods such as NH4EDTA and TCLP to determine the fate and therefore the risk of sludge-borne metals (Cd, Pb, Zn, Cu). The results show that the TCLP extraction method could potentially underestimate the impact of sewage sludge-borne metals when amended to agricultural soils. The extraction efficiency of the NH4EDTA and TCLP methods relative to the aqua regia extraction method was presented for Cd, Pb, Zn and Cu. The NH4EDTA extraction method seems to be an alternative to the aqua regia method, especially since the NH4EDTA measures the fraction of the metal that may become available in the environment. It is recommended that the aqua regia and NH4EDTA be used to classify and characterise the metal content of South African sludges.

Agriculture↗

Metal-on-metal: articulations for the new millennium.

Implants with metal-on-metal articulations (Metasul, Sulzer Medica, Winterthur, Switzerland [now Zimmer, Warsaw, IN]) have been used in nearly 300,000 total hip replacements. In three different clinical studies, clinical success has been demonstrated using this implant as measured by Harris hip scores, patient self-assessment, and assessment of mechanical complications. Of a study group of 924 patients who received this implant, the only reported complications were mechanical, incldding two cup loosenings (0.2%) and 36 dislocations (4.0%). In a randomized study, clinical resultsfor the group that received implants with metal-on-metal articulation were comparable to those of the ceramic-on-polyethylene (control) group. Reports assessing retrieved implants with metal-on-metal articulation demonstrate low annual linear wear rates and no consequences of elevated cobalt ion levels at follow-up from 4 years to 26 years. In light of these data, the continued ise of metal-on-metal articulations is recommended for any patient who does not have compromised renal function.

Arthroplasty, Replacement, Hip↗

Engineering issues and wear performance of metal on metal hip implants.

A major concern in total hip arthroplasty is the generation of polyethylene wear particles at the articulating surfaces and resulting macrophage mediated periimplant osteolysis. There is renewed interest in metal on metal bearings as a solution to this problem in view of their potential for greatly improved wear performance. Using a commercially available hip simulator, the wear performance of metal on metal femoral head and acetabular cup combinations was evaluated and various parameters affecting metal on metal implant wear were identified. Nine implants custom manufactured from 2 medical grades of CoCrMo alloy (ASTM F1537-95 and F75-92) were tested within bovine serum as the lubricant to 3 million cycles (equivalent to approximately 3 years of service in vivo). The progressive wear of the components was determined by gravimetric methods at approximately every 300,000 cycles. The wear rates were characterized by an initial period of accelerated wear after which a lower steady state wear rate was observed for subsequent cycles. The presence of calcium phosphate films on the component surfaces, the microstructure of the lower carbon, wrought alloy, and increased effective radii (decreased diametral clearances) were identified as factors that may be favorable to improved wear performance. The extent of the effect on wear of each parameter, however, cannot be discerned at this point and necessitates a study in which parametric changes are more tightly controlled. The present study suggests that the use of metal on metal articulating surfaces may mitigate the problem of osteolysis by offering improved wear performance.

Hip Prosthesis↗

Sandwich-like compounds based on the all-metal aromatic unit Al(4)2- and the main-group metals M (M=Li, Na, K, Be, Mg, Ca).

Inspired by the pioneering experimental characterisation of the all-metal aromatic unit Al(4)2- in the bimetallic molecules MAl4- (M=Li, Na, Cu) and by the very recent theoretical design of sandwich-type transition-metal complexes [Al4MAl4]q- (q=0-2; M=Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W), we used density functional theory (DFT) calculations (B3LYP/6-311+G(d) to design a series of novel non-transition-metal sandwich complexes based on the all-metal aromatic unit Al4(2-) and the main-group metals M (M=Li, Na, K, Be, Mg, Ca). The traditional homo-decked sandwich compounds [Al4MAl4]q- (without counterions) and (nM)q+[Al4MAl4]q- (with counterions M) (q=2-3, M=Li, Na, K, Be, Mg, Ca), although some of them are truly energy minima, have a much higher energy than many fused isomers. We thus concluded that it seems unlikely for Al4(2-) to sandwich the main-group metal atoms in the homo-decked sandwich form. Alternatively, we proposed a new type of sandwich complex, namely hetero-decked sandwich compounds [CpMAl4]q-, that are the ground-state structures for each M both with and without counterions. It was shown that with the rigid Cp- partner, the all-metal aromatic unit Al(4)2- might indeed act as a "superatom". These new types of all-metal aromatic unit-based sandwich complexes await future experimental verification.

Journal Article↗

Size, shape, and composition of wear particles from metal-metal hip simulator testing: effects of alloy and number of loading cycles.

There has been a revived interest in metal-metal total hip replacements because of their potential for improved wear performance compared with conventional metal-polyethylene implants. The aim of the present study was to characterize metal wear particles isolated from metal-metal hip simulator testing of various clinically relevant alloys and to analyze the effects of these alloys and the number of loading cycles on wear particle characteristics. Implants were manufactured using medical-grade cobalt-chromium-molybdenum (CoCrMo) alloys that were high-carbon wrought, low-carbon wrought, or cast (with solution annealing). Testing was performed in a MATCO orbital bearing hip simulator in 95% bovine calf serum. The wear particles were isolated from the serum at test periods of 0-0.25 million cycles (Mc) (run-in wear) and 1.75-2 Mc (steady-state wear) using an enzymatic protocol previously optimized to minimize particle changes due to reagents. Isolated particles embedded in epoxy resin were characterized by transmission electron microscopy (TEM) and energy dispersive X-ray analysis (EDXA). The EDXA results revealed the predominance of "lighter" particles containing Cr and O (most likely chromium oxide particles from the passivation layer) and fewer darker CoCrMo particles, with varying ratios of Co and Cr (possibly from carbides and from implant matrix material). More CoCrMo particles were observed with the low-carbon wrought alloy, but the majority of the particles for all three alloys was chromium oxides, especially for the 1.75-2 Mc test period. Image analysis of TEM micrographs revealed that for 0-0.25 Mc, there was up to 21% needle-shaped particles but that the majority remained round to oval in shape, reflecting the predominance of chromium oxide particles. Particle length averaged about 52 +/- 4 nm, with only small differences due to the alloy. For 1.75-2 Mc, most particles were round to oval in shape. They were even less needle-shaped than at 0.25 Mc, and they had a slightly smaller length, averaging 46 +/- 3 nm. In addition to characterizing the size and shape of particles from a MATCO simulator, this study is the first to demonstrate that particles that do not contain Co (presumably chromium oxides) can be predominant in the wear of metal-metal hip implants. It is therefore recommended that future in vitro and in vivo studies include the effects of these particles rather than just the effects of CoCrMo particles on the overall tissue response.

Alloys↗

Lack of correlation between trace metal staining and trace metal content of the rat hippocampus following colchicine microinjection.

Following the intrahippocampal injection of colchicine, the trace metal staining with Timm's method is shown to change in the hippocampus. The histochemical examinations were supplemented with atomic absorption spectrophotometric measurement of the trace metals (Zn, Fe, Cu). It was found that intrahippocampal colchicine treatment induces the temporary disappearance of the trace metal staining of the pyramidal cells of the regio superior, while there is a considerable reduction in the staining in the granular cells of the area dentata and in their mossy fibre terminals. Simultaneously, in contrast with the histochemical results, quantitative studies on the trace metal levels showed that colchicine does not lead to evacuation of the trace metals from the hippocampal formation. The combined atomic absorption and trace metal staining investigations prove that there is no correlation between the trace metal staining and the quantitative amounts of the trace metals.

Animals↗

Veterans Administration Cooperative Studies Project No. 147: association of metallic taste with metal ceramic alloys.

We examined patients to find out whether they noticed the prevalence of metallic taste and set out to determine the association of metallic taste with demographic, medical, and dental factors. Data were collected as part of a Veterans Administration Cooperative Study investigating the suitability of alternative metal ceramic alloys as substitutes for alloys that contain gold. Crowns and fixed partial dentures were made from control and alternative alloys for accepted volunteer patients. A month after placement of the restorations and at regularly scheduled recall appointments, the patients were asked if they tasted a metallic flavor. Of the 2023 times the question was asked, 101 positive responses were given by 68 patients (46 reported metallic flavor once, and 22 reported it more than once). Results indicated that youth, sensitivity to heat and cold, bruxism, grinding, and an increasing number of restorative units were significantly related to metallic taste. For any given visit, about 5% of the patients reported tasting a metallic flavor regardless of the type of alloy that was used in the restoration. Metallic taste does not appear to be a problem with alternative alloys.

Adult↗

Synthesis and evaluation of potential N pi and N sigma metal chelation sites within the beta-hydroxy-L-histidine subunit of bleomycin A2: functional characterization of imidazole N pi metal complexation.

The synthesis and evaluation of 4 and 5, fully functionalized deglycobleomycin A2 (2) analogues incorporating an oxazole and a pyrrole in place of the beta-hydroxy-L-histidine imidazole, are detailed. The oxazole agent is only capable of Npi metal complexation through a form related to the N1-H imidazole tautomer of bleomycin A2 (1) while the pyrrole agent may potentially mimic the Nsigma metal complexation capabilities of the imidazole N3-H tautomer. Metal complexes (Fe-II, Fe-III) of 4 and 5 were found to cleave duplex DNA in the presence of O2 (Fe-II) or H2O2 (Fe-III). The oxazole agent 4 which is incapable of Nsigma metal chelation was found to behave analogous to, albeit slightly less effectively than, deglycobleomycin A2 resulting in the characteristic 5'-GC/5'-GT sequence selective cleavage of duplex DNA directly confirming that imidazole/oxazole Npi metal chelation is sufficient for functional reactivity. Importantly, the effective substitution of the oxazole O-1 for the histidine N-1 further illustrates that this group does not require deprotonation upon metal complexation, oxygen activation, or the ensuing oxidation reactions, that the functional bleomycin A2 tautomer is the imidazole N'-H tautomer, and that the imidazole N'-H functionality is not contributing to the polynucleotide recognition through H-bonding to the phosphate backbone or nucleotide bases. In contrast, the pyrrole agent 5 which is incapable of Npi metal chelation, but possesses the capabilities of functioning as a Nsigma metal donor was also found to cleave duplex DNA, but does so in a nonsequence selective fashion with a significantly reduced efficiency and a diminished double to single strand cleavage ratio both only slightly above that of background iron itself. These observations are analogous to those made with 3 which lacks the imidazole altogether and further support the observations that Nsigma coordination, not Npi coordination, of the imidazole is required for the functional activity of bleomycin A2.

Antimetabolites, Antineoplastic↗

Three- to six-year results with the Ultima metal-on-metal hip articulation for primary total hip arthroplasty.

One hundred seventy-one primary total hip arthroplasties were evaluated in a prospective, randomized study. Ninety-five involved a metal-backed cup with an all-metal liner and 76 involved a metal-backed polyethylene cup that was used as the control. All were implanted with an S-ROM cementless femoral component with a 28 mm head. The mean follow-up period was 3.7 years (range, 3.0-5.7). The average postoperative Harris hip score was 95.4 (range, 65-100) for the metal-on-metal group and 96.1 (range, 65-100) for the metal-on-polyethylene group. Radiographic results were not statistically different between the 2 groups. Early results show the metal-on-metal articulation has been successful to date and justify continued clinical use.

Adolescent↗

Fluorescence study of the interaction of Suwannee River fulvic acid with metal ions and Al3+-metal ion competition.

In this study emission and synchronous-scan fluorescence spectroscopy have been used to investigate the interaction of the class A (oxygen seeking 'hard acid') metal Al(3+), with Suwannee River fulvic acid (SRFA), as well as competition between Al(3+) and several other metal ions (Ca(2+), Mg(2+), Cu(2+), Pd(2+), La(3+), Tb(3+) and Fe(3+)) for binding sites on SRFA. Of the four metal ions possessing very similar (and relatively low) ionic indices (Ca(2+), Mg(2+), Cu(2+) and Pd(2+)) only the latter two paramagnetic ions significantly quenched SRFA fluorescence emission intensity. Of the four metal ions possessing very similar (and relatively low) covalent indices (Ca(2+), Mg(2+), La(3+) and Tb(3+)) only the last paramagnetic ion (Tb(3+)) significantly quenched SRFA fluorescence. None of these metals was able to significantly compete with SRFA-bound Al(3+).Fe(3+), which differs substantially from all of the other metals examined in this study in that it possesses a relatively high ionic index (but not as high as Al(3+)) and a relatively low covalent index (but not as low as Al(3+)), was able not only to quench SRFA fluorescence but also to compete (at least to some extent) with SRFA-bound Al(3+). Synchronous-scan fluorescence SRFA spectra taken in the absence and presence of Fe(3+) and/or Al(3+) support the view that these two metal ions can compete for sites on SRFA. The results of these fluorescence experiments further confirm the Al(3+), and metal ions that have electronic properties somewhat similar to Al(3+) (such as Fe(3+)) are somewhat unique in their ability to interact strongly with binding sites on fulvic acids.

Journal Article↗

Changes in metallothionein concentrations in response to variation in natural factors (salinity, sex, weight) and metal contamination in crabs from a metal-rich estuary.

Intermoult male and female crabs Pachygrapsus marmoratus and Carcinus maenas were sampled from three sites between the mouth and 25 km upstream in the Gironde, the most Cd-contaminated estuary in France, in order to study the relative importance of natural factors (salinity, sex, weight) and accumulated metal concentrations on metallothionein (MT) concentrations. In the two species studied, higher metal, total protein and MT concentrations were observed in the hepatopancreas than in the gills. In P. marmoratus, MT concentrations were mainly related to changes in the natural factors even if MT and Zn concentrations were positively correlated in the hepatopancreas whereas in C. maenas, the main relationships were with accumulated metal levels. In the case of the natural factors, the most important ones were weight in gills of both crab species, and salinity changes in both hepatopancreas and gills of P. marmoratus. Cd and Cu concentrations in both organs of the two species were inversely related to salinity. The same observation was found for Zn concentrations in C. maenas but not in P. marmoratus. In the hepatopancreas of both species, the highest total protein concentrations were found in crabs from the site with the highest salinity, whereas there were no such differences in the gills. It seems that changes in MT concentrations are linked more to changes in general protein metabolism than to changes in metal accumulation. Thus it was important to examine the storage of metals in other tissue compartments, particularly the insoluble fraction which includes mineral granules which is known to also contribute to trace metal detoxification in invertebrates. In the gills of the crabs, Zn was present mainly in the insoluble fraction, whereas Cd was nearly equally distributed between soluble and insoluble fractions. In contrast, Cu in the gills and all three metals in the hepatopancreas of both species were mainly cytosolic, but this does not necessarily imply a predominant role for MT since the cytosolic fraction also includes other macromolecules which may be the target binding site for accumulated trace metals.

Journal Article↗

The effect of metal surface treatment on the shear bond strengths of base and noble metals bonded to enamel.

Adhesive resin luting agents provide a way for bonding metal surfaces to teeth through a combination of micromechanical retention to the rough metal surface and chemical adherence to metal oxides. The purpose of this study was to measure the effect of metal alloy surface treatments that would produce different textures and oxide layers on the shear bond strength of three alloys luted to etched enamel with one adhesive resin luting agent (Panavia). After a simulated porcelain firing sequence, high noble (Olympia), noble (Jelstar), and base metal (Rexillium III) alloy specimens were subjected to one of the following treatments: (1) sandblasting and simulated glazing, (2) simulated glazing only, (3) simulated glazing and sandblasting, or (4) simulated glazing, sandblasting, and tin plating. The specimens were bonded to extracted teeth and subjected to shear testing after water storage for 2 weeks, thermocycling for 500 cycles, and water storage for an additional 2 weeks. Data were analyzed with a two-way analysis of variance (alpha = 0.05). The base metal specimens and the tin-plated high noble and noble metal specimen groups exhibited similar mean shear bond strengths that were greater than the other groups. Those high noble and noble metal alloys sandblasted after simulated porcelain firing cycles and before the simulated glaze cycle exhibited nonsignificant increases in shear bond strengths compared with the groups that were either sandblasted after the simulated glaze cycle or not sandblasted at all.

Analysis of Variance↗

The distribution and intracellular compartmentation of metals in the endogeic earthworm Aporrectodea caliginosa sampled from an unpolluted and a metal-contaminated site.

The tissue distribution of Cd, Cu, Pb, Zn and Ca in the endogeic earthworm Aporrectodea caliginosa living in a non-polluted and a heavy metal polluted soil was investigated. The tissues of animals from the contaminated soil contained greater concentrations of Cd, Pb and Zn than the corresponding tissues of animals from the unpolluted soil. The greatest concentrations of Cd, Pb, Zn, and Ca were primarily accumulated within the posterior alimentary canal (PAC), a tissue fraction which contained the greatest proportion of the whole-worm burdens of the respective metals. Cu was distributed fairly evenly in the tissue fractions investigated. The pattern of accumulation for the 'heavy' metals is broadly similar to that for epigeic earthworms; in contrast, a different pattern of tissue accumulation was found for Ca. In animals from the uncontaminated site, the major elemental constituents of the chloragosomes were P, Ca, Zn and S. A significant positive correlation exists between P and Ca within the chloragosomal matrix. These intracellular vesicles are major foci for Pb and Zn accumulation within the PAC, with 'excess' metals associated with P ligands within the chloragosome matrix. The incorporation of Pb and Zn appears to involve the cationic displacement of Ca. Such compartmentation appears to prevent dissemination of large concentrations of these metals into other earthworm tissues, and may thus represent a detoxification strategy based on accumulative immobilization. No intracellular localization of Cd was identified in the study, although the Cd concentration in the metalliferous soils examined was not exceptionally high. The observations are discussed in the context of a contribution to enhanced understanding of metal ecotoxicology in earthworms by providing baseline data on a little investigated ecophysiological group of earthworms. Comparisons of metal distribution and mechanisms of metal sequestration are made with other ecophysiological groups of earthworms, and the significance of the findings to biomonitoring and toxicity-testing programmes is considered.

Journal Article↗

Failure of a metal-on-metal total hip arthroplasty from progressive osteolysis.

Ultra-high-molecular weight polyethylene (UHMWPE) wear, debris-induced osteolysis is a frequent cause of failure of total hip arthroplasty. Metal-on-metal total hip arthroplasty eliminates the generation of UHMWPE particulate debris. Although the volumetric wear of a metal-on-metal articulation may be lower than a metal-UHMWPE articulation, the number of particles may be higher. Osteolysis can develop in response to metallic and UHMWPE debris. The following case of massive osteolysis associated with large amounts of cobalt-chrome wear debris shows adhesive and abrasive wear mechanisms, as well as wear caused by third-body cobalt-chrome debris and impingement of the femoral component against the rim of the acetabular cup, which led to failure of a metal-on-metal total hip arthroplasty.

Aged↗

Understanding how cells allocate metals using metal sensors and metallochaperones.

Each metalloprotein must somehow acquire the correct metal. We review the insights into metal specificity in cells provided by studies of ArsR-SmtB DNA binding, metal-responsive transcriptional repressors, and a bacterial copper chaperone. Cyanobacteria are the one bacterial group that have known enzymatic demand for cytoplasmic copper import. The copper chaperone and ATPases that supply cyanobacterial plastocyanin and cytochrome oxidase are reviewed, along with related ATPases for cobalt and zinc. These studies highlight the contributions of protein-protein interactions to metal speciation. Metal sensors and metallochaperones, along with metal transporters and metal-storage proteins, act in concert not only to supply the correct metals but also to withhold the wrong ones.

Biological Transport↗

A systematic study of CO oxidation on metals and metal oxides: density functional theory calculations.

CO oxidation on Ru(0001), Rh(111), Pd(111), Os(0001), Ir(111), Pt(111), and their corresponding metal oxides is studied using density functional theory. It is found that (i) the reactivity of metal oxide is generally higher than that of the corresponding metal, and (ii) on both metals and metal oxides, the higher the chemisorption energy is in the initial state, the larger the reaction barrier. The barriers are further analyzed by decomposing them into electronic and geometric effects, and the higher reactivity of metal oxides is attributed mainly to the surface geometric effect. Moreover, the electronic effect on both metals and metal oxides follows the same pattern: the shorter the OC-O bond distance in the TS, the higher the barrier.

Journal Article↗

Oligothiophene bipyridine alternate copolymers and their ruthenium metalated analogues: in situ ESR and UV-vis investigations of metal-chain interactions.

In situ electron spin resonance (ESR) and UV-vis spectro-electrochemical studies have been performed on two copolymers consisting of alternating subunits of regioregular head to tail (HT) coupled 3-octylthiophene tetramer and 2,2'-bipyridine subunits (P4) or 3-octylthiophene hexamer subunits of the same regioregularity and 2,2'-bipyridine subunits (P6). Both P4 and P6 have been investigated in their metal-free form as well as in the ruthenium(II) metalated form (P4-Ru and P6-Ru). P4 and P6 in the p-doped state exhibit a clear ESR signal characteristic of the presence of polarons in the oligothienylene subunits. In the case of P4, no recombination of polarons into bipolarons is observed, whereas the recombination process takes place in P6. The formation of bipolarons is well-rationalized in terms of the conjugation length, and it seems clear that the higher length of the oligothiophene subunit in P6( )()stabilizes bipolarons(.)() The same effect, is induced by the coordination of -Ru(bpy)(2)(2+) to the bipyridine unit in the metalated form of both polymers, which results in an increase of the conjugation length. Important information is gained from the analysis of the ESR spectra of both nonmetalated and metalated in the oxidized (p-doped) and reduced (n-doped) forms. In the p-doped state both nonmetalated and metalated polymers reveal the presence of a narrow ESR line characteristic of the mobile spin carriers in the polymer matrix. The oxidation of the metal center occurs at higher potentials and leads to an irreversible destruction of the system. To the contrary, in the reduced (n-doped) state the ESR lines of the nonmetalated and metalated polymers markedly differ. A significant line broadening with simultaneous change of the g-value is caused by spin-orbit coupling phenomenon induced by the presence of the coordinating metal. Finally, the observation of a clear polaronic band in the UV-vis spectrum of p-doped P4 and its strong dependence on the applied potential can be clearly correlated with the potential induced changes in the ESR spin density. The same applies to P4-Ru, where the changes in the polaronic and bipolaronic bands can also be correlated with the ESR spin density changes.

Journal Article↗

Comparison of UV and visible Raman spectroscopy of bulk metal molybdate and metal vanadate catalysts.

The visible (532 and 442 nm) and UV (325 nm) Raman spectra of bulk mixed metal oxides (metal molybdates and metal vanadates) were compared on the same spectrometer, for the first time, to allow examination of how varying the excitation energy from visible to UV affects the resulting Raman spectra. The quality of the Raman spectra was found to be a strong function of the absorption properties of the bulk mixed oxide. For bulk mixed metal oxides that absorb weakly in the visible and UV regions, both the visible and UV Raman spectra were of high quality and exhibit identical vibrational bands, but with slightly different relative intensities. For bulk mixed metal oxides that absorb strongly in the UV and visible regions and/or strongly in the UV and weakly in the visible regions, the visible Raman spectra are much richer in structural information and of higher resolution than the corresponding UV Raman spectra. This is a consequence of the strong UV absorption that significantly reduces the sampling volume and number of scatterers giving rise to the Raman signal. The shallower escape depth of UV Raman, however, was not sufficient to detect vibrations from the surface metal oxide species that are present on the outermost surface layer of these crystalline mixed metal oxide phases as previously suggested. It was also demonstrated that there is no sample damage by the more energetic UV excitation when very low laser powers and fast detectors are employed, thus avoiding the need of complicated fluidized bed sample arrangements sometimes used for UV Raman investigations. The current comparative Raman investigation carefully documents, for the first time, the advantages and disadvantages of applying different excitation energies in collecting Raman spectra of bulk mixed metal oxide materials.

Journal Article↗