Pathology of enteric infections induced by the acanthocephalan Profilicollis chasmagnathi in Olrog's gull, Larus atlanticus, from Argentina.

Acanthocephalans can be pathogenic helminths of marine birds. Every year during the breeding season, there is variable mortality among prefledged chicks from the largest known Olrog's gull (Larus atlanticus) colony. Mortality has been associated with infection by the acanthocephalan Profilicollis chasmagnathi. Our aim was to study the role of chicks' size as a risk factor for intensity of infection and severe pathology, and to expand upon previous pathological findings reported in acanthocephalan-infected chicks. Size of the chick was associated with intensity of infection and number of intestinal perforations, which increased by 6.9% and 4.1%, respectively, for each millimetre increment in chick size. Infection was associated with inflammatory enteritis and granulomatous peritonitis. Complete intestinal perforations were observed in 85% and 97.3% of the studied chicks in 2005 and 2006, respectively, and they were observed very early during the post-hatching period. Our results show: (1) the presence of advanced pathology associated with acanthocephalan infections in chicks, beginning very early in the post-hatching period; and (2) significant increases in the intensity of infection and the associated pathology as a function of size of chicks, in dead chicks during this period.

Epidemiology of acanthocephalan infections in crabs from the Bahía Blanca Estuary, Argentina.

This study was conducted in two populations of crabs, Cyrtograpsus angulatus and Neohelice granulata from the Bahía Blanca Estuary, in Argentina, to identify risk factors for infection by the acanthocephalan Profilicollis chasmagnathi and to assess the association between infection and mortality of these hosts. Cyrtograpsus angulatus and N. granulata crabs were sampled seasonally over the course of a year, and spring sampling included collection of dead crabs predated by Olrog's gulls in a nearby breeding colony. Potential risk factors for infection were assessed and the number of cystacanth larvae per crab was counted. In C. angulatus, the odds of infection increased by 7% for each millimetre increase in carapace length, and were nearly 17 times greater in crabs sampled from the Olrog's gull feeding area compared with those sampled from nests in the breeding colony. For every millimetre increase in carapace length in N. granulata, the odds of infection increased by 13% in crabs from the breeding colony, and by 32% in crabs from the feeding area. Mean intensity of infection in N. granulata increased by 16.5% for each additional millimetre of carapace width. The level of parasite aggregation was lowest in the largest C. angulatus and highest in N. granulata predated by Olrog's gull. The results show that host size is the most important factor influencing infection prevalence in both crab species and intensity of infection in N. granulata, and suggest the presence of parasite-induced mortality in the populations studied.

New insights on the mechanism of oxidation of D-galacturonic acid by hypervalent chromium.

The pollutant Cr(VI) is known to be very carcinogenic. In conditions of excess of Cr(VI), oxidation of D-galacturonic acid (Galur), the major metabolite of pectin, yields d-galactaric acid (Galar) and Cr(III). The redox reaction takes place through a multistep mechanism involving formation of intermediate Cr(II/IV) and Cr(V) species. The mechanism combines one- and two-electron pathways for the reduction of Cr(IV) by the organic substrate: Cr(VI)→ Cr(IV)→ Cr(II) and Cr(VI)→ Cr(IV)→ Cr(III). This is supported by the observation of the optical absorption spectra of Cr(VI) esters, free radicals, CrO(2)(2+) (superoxoCr(III) ion) and oxo-Cr(V) complexes. Cr(IV) cannot be directly detected; however, formation of CrO(2)(2+) provides indirect evidence for the intermediacy of Cr(II/IV). Cr(IV) reacts with Galur much faster than Cr(V) and Cr(VI) do. The analysis of the reaction kinetics via optical absorption spectroscopy shows that the Cr(IV)-Galur reaction rate inversely depends on [H(+)]. Nevertheless, high [H(+)] still does not facilitate accumulation of Cr(IV) in the Cr(VI)-Galur mixture. Cr(VI) and the intermediate Cr(V) react with Galur at comparable rates; therefore the build-up and decay of Cr(V) accompany the decay of Cr(VI). The complete rate laws for the Cr(VI), Cr(V) and Cr(IV)-Galur redox reaction are here derived in detail. Furthermore, the nature of the five-co-ordinated oxo-Cr(V) bischelate complexes formed in Cr(VI)-Galur mixtures at pH 1-5 is investigated using continuous-wave and pulsed electron paramagnetic resonance (EPR) and density functional theory (DFT).

The reduction of CrVI to CrIII by the alpha and beta anomers of D-glucose in dimethyl sulfoxide. A comparative kinetic and mechanistic study.

The reduction of CrVI by alpha-D-glucose and beta-D-glucose was studied in dimethyl sulfoxide in the presence of pyridinium p-toluensulfonate, a medium where mutarotation is slower than the redox reaction. The two anomers reduce CrVI by formation of an intermediate CrVI ester precursor of the slow redox step. The equilibrium constant for the formation of the intermediate chromic ester and the rate of the redox steps are different for each anomer. alpha-D-Glucose forms the CrVI-Glc ester with a higher equilibrium constant than beta-D-glucose, but the electron transfer within this complex is slower than for the beta anomer. The difference is attributed to the better chelating ability of the 1,2-cis-diolate moiety of the alpha anomer. The CrV species, generated in the reaction mixture, reacts with the two anomers at a rate comparable with that of CrVI. The EPR spectra show that the alpha anomer forms several linkage isomers of the five-coordinate CrV bis-chelate, while beta-D-glucose affords a mixture of six-coordinate CrV monochelate and five-coordinate CrV bis-chelate. The conversion of the CrV mono- to bis-chelate is discussed in terms of the ability of the 1,2-cis- versus 1,2-trans-diolate moieties of the glucose anomers to bind CrV.