Chromium bioavailability in aquatic systems impacted by tannery wastewaters. Part 2: New insights from laboratory and in situ testing with Chironomus riparius Meigen (Diptera, Chironomidae).

Chromium is widely used as a tanning agent and can become a contaminant of concern in aquatic ecosystems receiving discharges from industrial or artisanal tanning activities. In a companion study, we showed that Cr discharged by tanneries was bioavailable to indigenous chironomids with accumulation via sediment ingestion likely to represent the predominant exposure route. However, Cr accumulation by chironomids did not directly reflect the degree of sediment contamination and the potential adverse effects of Cr accumulation on chironomids were not evaluated. In the present study, chironomids were exposed to homogenised, field-collected sediments in the laboratory and to intact sediments in situ using a customized caging system. Chromium concentrations were assessed in sediments, exposed larvae of laboratory-reared Chironomus riparius and overlying waters of in situ cages. Experimental results of Cr bioaccumulation were compared with expected Cr body burden in chironomids calculated using biodynamic modelling. Our data provided strong support to the hypothesis that Cr bioaccumulation in the field is specifically controlled by the deposition of contaminated suspended particulate matter (SPM) containing a pool of Cr readily bioavailable to surface deposit feeders. Considering freshly deposited SPM as an additional route of exposure for surface deposit feeders leads to a good agreement between the modelling and experimental results. Additionally, a Cr body burden of about 77 µg g-1 d.w. was identified as a tentative threshold above which effects on the growth of C. riparius may appear. While both laboratory and in situ experiments provide evidence for the availability of Cr in aquatic system impacted by tannery wastewaters, standard laboratory exposure conditions may miss additional exposure routes in the field and underestimate possible adverse effects on benthic organisms.

Chromium bioavailability in aquatic systems impacted by tannery wastewaters. Part 1: Understanding chromium accumulation by indigenous chironomids.

The tanning industry uses large quantities of Cr whose contribution to the contaminant burden of aquatic organisms is not yet fully understood. The present study investigated Cr bioaccumulation by indigenous chironomids in a freshwater ecosystem impacted by tannery effluents. Total Cr content in sediments and in chironomids was determined on several occasions. Chromium distribution among sediments and pore waters, and Cr speciation in overlying and pore waters were studied in detail to understand possible factors controlling Cr bioavailability to chironomids. Total chromium concentration ranged from 69 to over 3000 µg g-1 dry weight in sediments and from negligible to over 300 µg g-1 dry weight in chironomids (values corrected for sediment gut content). Filterable (<0.45 µm) Cr concentration in overlying waters and pore waters from the surface sediment layers (upper 2 cm) ranged from 3 to 120 µg L-1, with Cr(VI) representing 0.5-28% of the total filterable Cr. Chromium profiles in pore waters as determined by diffusive equilibration in thin films (DET) and diffusive gradient in thin films (DGT) were comparable. DGT-labile Cr accounted for <2% of the total Cr measured by DET. Although Cr concentrations in sedimentary and aqueous matrices were not directly proportional to Cr levels measured in chironomids, the available findings suggested that Cr inputs from tanneries were bioavailable to resident chironomids. These observations are of particular importance considering that Cr(III), putatively of limited bioavailability and ecotoxicological concern, is the predominant redox form of Cr in bed sediments impacted by tannery discharges. The companion paper provides further insight into Cr bioavailability and effects in tannery impacted ecosystems using a combination of in situ and laboratory approaches.

Complications associated with the treatment of fractures of the dentate portion of the mandible in paediatric patients: a systematic review.

This study aimed to answer the following question: What is the best treatment option for fractures of the dentate portion of the mandible in paediatric patients when considering the occurrence of postoperative complications? A systematic literature review was done using the PubMed, Scopus, and Cochrane Library databases, and 1186 articles on the topic were found. Twelve of these articles were included in the final review after the full texts had been read. A sample of 178 paediatric patients was obtained. In the six cases in which treatment was surgery with titanium plate fixation, there were no postoperative complications, whereas in the 141 cases in which treatment was surgery with biodegradable plates, there were 12 postoperative complications, and in the 31 cases in which treatment was non-surgical, there were three postoperative complications. A connection between the best treatment and the number of postoperative complications in fractures of the dentate portion of the mandible in paediatric patients could not be established; however, the occurrence of postoperative complications was low for both surgical and non-surgical treatments.

Aesthetic and functional implications following rotation of the maxillomandibular complex in orthognathic surgery: a systematic review.

The manipulation of the maxillomandibular complex (MMC) in orthognathic surgery has been used widely in the treatment of dentofacial deformities so as to optimize aesthetic and functional results, making these more stable in the long term. The aim of the present study was to perform a systematic literature review of the aesthetic and functional implications following rotation of the occlusal plane in orthognathic surgery, by evaluating skeletal stability, facial harmony, respiratory function, and temporomandibular joint (TMJ) function after clockwise or counterclockwise rotation of the MMC. A survey of Scopus, PubMed, and Cochrane databases was performed through which 10 papers were selected for the final review. From this review, it could be concluded that facial aesthetics, TMJ function, and skeletal and occlusal stability in the orthosurgical treatment of dentofacial deformities may be influenced by the surgical manipulation of the MMC (clockwise or counterclockwise rotation). However, although this treatment technique is used widely today, the results of the present study do not provide sufficient scientific evidence with regard to the choice of this approach.

Postoperative infection associated with mandibular angle fracture treatment in the presence of teeth on the fracture line: a systematic review and meta-analysis.

The aim of this review was to answer the question: Which is the best procedure to follow when there is tooth involvement in the line of mandibular angle fracture, taking into consideration the occurrence of postoperative infection? A systematic literature review using the PubMed (MEDLINE), Virtual Health Library (VHL), Cochrane Library, and Scopus databases was done, and a total of 1007 articles were found. Among these, 13 articles were included in the final review after the papers were read. A series of 1542 mandibular angle fractures with the presence of teeth in the fracture line was obtained. Of 788 cases where the tooth was removed, a postoperative infection occurred in 84 cases; of 754 cases where the tooth was retained, postoperative infection also occurred in 84 cases. Through this review it was observed that there was no significant statistical difference between removing or retaining the tooth in the line of fracture and the occurrence of postoperative infection.

Diabetes aggravates acute pancreatitis and inhibits pancreas regeneration in mice.

AIMS/HYPOTHESIS: It is well established that acute pancreatitis often causes diabetes and that a high blood glucose level associated with pancreatitis is a marker of poor prognosis. The aim of this study was to evaluate if diabetes merely reflects the severity of pancreatitis or whether it can also aggravate the progression of this disease in a vicious circle. METHODS: Reversible acute oedematous pancreatitis was induced in untreated and streptozotocin-treated diabetic mice by injection of cerulein. Progression of pancreatitis was studied by immunohistochemistry, ELISA and various other enzyme assays. The production of regenerating islet-derived 3ß (REG3ß) was determined by western blot and immunohistochemistry. RESULTS: While cerulein treatment in non-diabetic mice resulted in acute pancreatitis followed by regeneration of the pancreas within 7 days, diabetes aggravated pancreatitis, inhibited the regeneration of the exocrine tissue and led to strong atrophy of the pancreas. The aggravation of pancreatitis by diabetes was characterised by decreased production of the anti-inflammatory protein REG3ß, increased inflammation, augmented oedema formation and increased cell death during the acute phase of pancreatitis (p < 0.05). During the regenerative phase, diabetes augmented inflammation, increased cell death, reduced acinar cell expansion and increased the expansion of duct as well as interstitial cells, resulting in the formation of tubular complexes (p < 0.05). Administration of insulin reversed the observed phenotype in diabetic mice. CONCLUSIONS/INTERPRETATION: Diabetes aggravates acute pancreatitis and suppresses regeneration of the exocrine tissue. Thus, diabetes is not just a concomitant phenomenon of pancreatitis, but can have a fundamental influence on the progression of acute pancreatitis.

Electrochemical identification of corrosion products on historical and archaeological bronzes using the voltammetry of micro-particles attached to a carbon paste electrode.

An overview of the electrochemical method for the identification of microsampled corrosion products from historical and archaeological bronzes is reported. Two characteristic examples of long-term air and subterranean formed patinas and two artificial patinas formed on Cu-6%Sn bronze in sulphate and chloride solutions, were investigated in 0.1M HCl(aq) by means of the cyclic voltammetry of micro-particles attached to a carbon paste electrode. Patina constituent phases were identified by comparing the electrochemical parameters of the patina samples to those of reference compounds: CuO, Cu(2)O, SnO, SnO(2), CuCl, CuCl(2) x 2H(2)O and CuSO(4) x 5H(2)O. An identification scheme was suggested which may be applied to discern the various corrosion products of bronze based on electrochemical data (voltammetric peak potentials). The presence of two prevalent phases of sulphate and chloride patinas, CuSO(4) and CuCl, as well as the presence of Sn compounds was clearly indicated by the cyclic voltammetry of microparticles, in both, naturally and artificially formed samples. A comparison to the ATR-FTIR results revealed that the methods are complementary and that their simultaneous application could prove particularly valuable in drawing conclusions about the current shape and prospects of the conservation and restoration of bronze artefacts.

Application of a bismuth film electrode to the voltammetric determination of trace iron using a Fe(III)-TEA-BrO3- catalytic system.

A sensitive catalytic voltammetric method for determining trace iron at a bismuth film electrode (BiFE) is described. The method is based on the cathodic reduction of the Fe(III)-triethanolamine (TEA) complex to Fe(II). It has been proved that the addition of KBrO3 causes rapid oxidation of Fe(II) and TEA, and therefore results in a large increase in the analytical signal from Fe(III) when TEA is placed in alkaline solution. When TEA was present in the solution, operating the BiFE under optimized conditions yielded a stable catalytic voltammetric response for iron, with high sensitivity (0.88 muA muM(-1)), good precision (RSD=3.9%) and a low detection limit (7.7 x 10(-9) M), obtained without any preconcentration procedure. Possible interferences from the coexisting ions and surface-active substances were investigated. Finally, the method was applied with satisfactory results to the determination of iron in certified reference river water samples.

Catalytic adsorptive stripping voltammetry versus electrothermal atomic absorption spectrometry in the determination of trace cobalt and chromium in human urine.

Two methods of the determination of cobalt and chromium in human urine of non-occupationally exposed populations-highly sensitive catalytic adsorptive stripping voltammetry (CAdSV) and electrothermal atomic absorption spectrometry (ET-AAS)-are evaluated and compared. The CAdSV methods are based on adsorptive accumulation of a cobalt-nioxime (1,2-cyclohexanedione dioxime) or a chromium-DTPA (diethylenetriammine-N,N,N',N'',N''-pentaacetic acid) complexes on a hanging mercury drop electrode, followed by a stripping voltammetric measurement of the catalytic reduction current of the adsorbed complex in the presence of sodium nitrite in case of cobalt or in the presence of sodium nitrate in case of chromium determination. In the CAdSV procedure UV-photolysis was used for the sample pre-treatment; the ET-AAS determination did not require any separate preliminary decomposition of the analyte urine samples. The accuracy of the procedures was checked by the analysis of commercially available quality control urine samples. The detection limits (3sigma) were 0.13mugl(-1) for Co and 0.18mugl(-1) for Cr in ET-AAS determination and 0.007mugl(-1) for Co and 0.002mugl(-1) for Cr in CAdSV measurements. Precision (R.S.D.) was less than 5% for both methods. The study has shown that the CAdSV is a more reliable and sensitive technique for the determination of very low cobalt and chromium contents in urine, the detection of which is not possible when using the AAS technique.

A note on distributions of times to coalescence, under time-dependent population size.

Expressions for marginal distributions of times in the time-varying coalescence process are derived. The proposed method allows also for computation of joint probability distribution for pairs, triples, etc. of coalescence times. The expressions derived are useful for (1) extending several statistics from time constant to time-varying case, (2) increasing efficiency and accuracy of simulations in time-varying evolution, and (3) debugging coalescence simulation software.

Determination of arsenic in water--quality assurance and calculation of metrological characteristics.

Arsenic is a toxic element, acting as a nerve poison and proven carcinogen. Its main source for humans is drinking water where the most important are arsenic (V) compounds. With respect to the Slovak standard, in force since 1998, the maximum tolerable value is defined as the important characteristic of drinking water. If the value 0.01 mg.l-1 of arsenic is exceeded, water is not drinkable. The mentioned standard defines criteria for precision of the arsenic determination and the corresponding limit of detection--being 10% of the maximum tolerable value. Arsenic content in the drinking water samples was measured by the AAS method. Internal Quality Control for analysis by the ETA AAS method was based on the harmonised guidelines recommended by IUPAC, ISO and AOAC. The following metrological characteristics were calculated: precision, accuracy, and the yield of the arsenic standard addition to the studied sample--matrix spike and analytical spike. In addition to it, a thorough study of the limit of detection, LOD, and the limit of quantification (determination), LOQ, was performed. The LOD and LOQ values were calculated in the traditional way as well as by the ULA technique, newly recommended by IUPAC. In the latter case, the calculated LOD value was close to the demanded 10% limit of the maximum tolerable value, which is 1 microgram.l-1 As. The repeatability and reproducibility, found at two concentration levels 56.02 +/- 0.73 micrograms.l-1 and 6.0 +/- 0.9 microgramsl-1, were 3.2% and 3.9%, respectively, and 7.1% and 9.8%, respectively. Trueness of the applied AAS method was proven satisfactory on the reference material SRM 1643 Trace Elements in Water.

Electrochemical and spectroscopic investigation of the reduction of dimethylglyoxime at mercury electrodes in the presence of cobalt and nickel.

Voltammograms (polarograms) obtained from solutions of cobalt and nickel containing dimethylglyoxime (dmgH(2)) are widely used for the trace determination of these metals. Detailed electrochemical and spectroscopic studies on the reduction process observed in the analytically important ammonia buffer media at mercury dropping, hanging, and pool electrodes are all consistent with an overall 10-electron reduction process, in which both the dmgH(2) ligand and cobalt ions are reduced in the adsorbed state: Co(II) + 2dmgH(2) ⇌ (solution) [Co(II)(dmgH)(2)] + 2H(+); [Co(II)(dmgH)(2)] + Hg ⇌ (electrode) [Co(II)(dmgH)(2)](ads)Hg; and [Co(II)(dmgH)(2)](ads)Hg + 10e(-) + 10H(+) → Co(Hg) + 2[2,3-bis(hydroxylamino)butane]. The limited solubility of the nickel complex in aqueous media restricts the range of studies that can be undertaken with this system, but an analogous mechanism is believed to occur. Low-temperature voltammetric studies in dichloromethane at a frozen hanging mercury drop electrode and in situ electron spin resonance electrochemical measurements on more soluble analogues of the dimethylglyoxime complexes are consistent with an initial one-electron reduction step being available in the absence of water. Deliberate addition of water to acetone solutions enables the influence of the aqueous environment on voltammograms and polarograms to be examined. The results of the present study are compared with the wide range of mechanisms proposed in other studies.

Application of catalytic adsorptive stripping voltammetry of the cobalt-alpha-benzil dioxime complex to analysis of cobalt traces in metallic zinc.

The catalytic adsorptive stripping voltammetric method with alpha-benzil dioxime and nitrite affords numerous advantages in cobalt determination. The detailed conditions of the determination of the cobalt traces in metallic zinc by catalytic adsorptive stripping voltammetry have been investigated. Both the linear sweep and the differential pulse stripping modes can be used with similar sensitivity. Possible interferences by Mn, Pb, Cu, Ni and Fe are evaluated. In the presence of 5 x 10(5) fold excess of Zn the linear dependence of the cobalt CASV peak current on concentration ranged from 0.05 mug/l to 3 mug/l. Optimal conditions include the accumulation potential of -0.65 V and the accumulation time of 10 sec. The results of the determination of 10(-5)% level of Co in the metallic zinc showed good reproducibility (relative standard deviation, RSD = 0.07) and reliability.

Adsorptive voltammetric determination of copper as its nioximate complex.

A sensitive and selective stripping voltammetric ultratrace determination of copper is described, based on adsorptive accumulation of the cu(II)-nioxime complex on the surface of a hanging mercury drop electrode, followed by the reduction of the adsorbed complex during the cathodic scan. The analytical conditions for the determination of copper by differential-pulse and linear-scan absorption voltammetry have been optimized. The method is compared to the routine anodic stripping voltammetric method for copper. Its applicability to river and potable water analysis is illustrated. The detection limit, restricted by the blank, is about 0.5 microg/l.; the relative standard deviation (at microg/l. level) for a standard solution is below 5% and for water samples is 5-9%.

[Fine-needle biopsy in the early diagnosis of thyroid neoplasms]. / Biopsja cienkoiglowa we wczesnym rozpoznawaniu nowotworów tarczycy.

Among the patients directed to the Department of Endocrinology of the Institute of Internal Medicine for diagnostic examinations of the thyroid, 726 (647 women and 79 men, of age between 16 and 79 years) were qualified to surgery after scintigraphic detection of cold nodules. From this group, 474 patients had thin-needle biopsy specimens taken for cytologic examination. The results of the latter examinations have been compared with those of histologic examination performed on the tissue removed during surgery. The occurrence of a malignant tumor (in 99.1%--thyroid cancer) was found in 108 patients (22.8%) from the group having thin-needle biopsy performed. Comparison of the results of cytologic examination with those of postoperative histologic examination demonstrated low sensitivity of biopsy examination (50.0%), as opposed to high specificity (96.2%) and high accuracy (85, 3%). Analysis of the false-negative results (54/108) revealed that the main causes of errors are difficulties in differentiation of adenoma from follicular carcinoma. Widening of the indications to surgery by a group of patients with adenoma will increase sensitivity to 84.8% and will require including into the operated group of about 50% of patients with scintigraphically diagnosed cold nodules: The introduction of the new term: "urgent strumectomy", has been proposed; also a diagnostic algorithm, useful for early diagnosis of malignant tumors of the thyroid, has been discussed.