Metal speciation dynamics and bioavailability: bulk depletion effects

Under conditions of bulk depletion, the speciation and bioavailability of trace metals must be considered at two different time scales: (i) the time scale of the biouptake flux, as determined by diffusion of the bioactive free metal, dissociation of the bioinactive complex species, and the internalization rate; and (ii) the time scale of depletion of the bulk medium. The implications of these two time scales for the speciation dynamics are discussed in terms of experimental conditions. The geometry of the system is taken into accountvia a spherical cellular model. It considers a spherical organism depleting a spherical volume in a nonstirred medium and assumes linear adsorption of the metal atthe biointerface and first-order internalization kinetics. In cases where the rate of biouptake is fully controlled by the internalization step, concentration gradients in the medium are insignificant. Then the biouptake becomes independent of the geometry of the system, and the model has a much simpler solution. Examples of trace metal uptake by microorganisms are analyzed: (i) cobalt uptake by Prochlorococcus in the presence of NTA, under conditions where bulk depletion is the controlling process due to the large number of organisms and high internalization rates, (ii) silver uptake by Chlamydomonas reinhardtii with significant effects of bulk depletion, due to the high internalization rate; (iii) lead uptake by Chlorella vulgaris with pratically negligible bulk depletion due to the low internalization rate of the metal; and (iv) lead uptake by intestinal Caco-2 cells, illustrating the simplification of the bulk depletion model for a system with different geometry where internalization is the rate-controlling step.     

Seasonal changes in phospholipids of mussel (Mytilus edulis Linne)

The phospholipids of mussels (Mytilus edulis Linne) from the coast of Qingdao were extracted, fractionated and analysed over a 12 month period. The contents of total lipids, neutral lipids, polar lipids and phospholipids were measured. The composition of phospholipids was determined by high‐performance liquid chromatography, and their fatty acid composition was analysed by gas chromatography. The phospholipid content ranged from 3.6 to 6.4 g kg^?1 soft tissue. PE (phosphatidyl ethanolamine) and PC (phosphatidyl choline) were the major constituents. C16:0, C20:5 and C22:6 were the major fatty acids. C20:5 (5.25–23.10%) and C22:6 (6.05–20.42%) varied regularly with the seasonal factors. Their total amounts were high from January to June, which would be an optimal time for the utilisation of the phospholipids of mussels. © 2002 Society of Chemical Industry     

Uptake of sediment-bound bioavailable polychlorobiphenyls by benthivorous carp (Cyprinus carpio)

It is unclear whether accumulation of sediment-bound chemicals in benthivorous fish depends on the degree of sequestration in the sediment like it does for invertebrates. Here, we report on the potential of slow and fast desorbing sediment-bound polychlorobiphenyl (PCB) fractions for accumulation in carp (Cyprinus carpio) in lake enclosures treated with different nutrient doses. Routes of PCB uptake were quantitatively evaluated for 15 PCBs (log Kow range 5.6-7.8) using model analysis. Fast-desorbing PCB fractions in the sediment were defined as the ratio of 6-h Tenax-extractable to (total) Soxhlet-extractable concentrations. These fractions varied between 4 and 22% and did not show a clear trend with log Kow. However, bioaccumulation of PCBs in carp correlated much better with Tenax-extractable concentrations than with total-extractable concentrations. Nutrient additions in the enclosures had a positive effect on PCB accumulation. Model results showthat PCB uptake in carp can be explained from (1) uptake through invertebrate food, (2) uptake from fast-desorbing fractions in ingested sediments, and (3) uptake from water, where PCBs are in partitioning equilibrium with fast-desorbing fractions. The main implication of this research is that fast-desorbing PCB fractions in sediments have great predictive potential for bioaccumulation in benthivorous fish.     

Depuration of cadmium from blue mussel (Mytilus edulis) by hydrolysis peptides and chelating metal elements

The present experiment was conducted to investigate the effects of prepared hairtail (Lepidopusc audatus) hydrolysis peptide–metal element (Fe^2 +, Zn^2 +, Ca^2 +, or Mg^2 +) complexes (PH–Fe^2 +, PH–Zn^2 +, PH–Ca^2 +, or PH–Mg^2 +) on the depuration of cadmium (Cd) from blue mussel (Mytilus edulis) tissues. Cd concentrations in anterior adductor muscle, posterior adductor muscle, gill, mantle, and visceral mass of mussels were 11.391, 15.323, 63.672, 19.509, and 109.621 μg/g, respectively, after 5 days of exposure to 0.32 mg/L Cd. Five groups of these exposed mussels were then exposed to seawater laced with four different concentrations of the peptide complexes listed above (5, 10, 15, and 20 mg/L) for 8 days. After 8 days of depuration, 5 mg/L of PH–Fe^2 +, PH–Zn^2 +, and PH–Ca^2 + showed no significant (P > 0.05) effects on Cd concentrations in mussel tissues. However, significant differences (P < 0.05) were observed in groups exposed to 20 mg/L of PH–Fe^2 +, PH–Zn^2 +, and PH–Ca^2 +. The Cd concentrations in anterior adductor muscle, posterior adductor muscle, gill, mantle, and visceral mass were significantly (P < 0.05) decreased by 29.56–35.83%, 27.51–33.62%, 31.59–40.34%, 25.83–31.28%, and 33.62–33.97%, respectively. Nevertheless, the variables of Cd concentrations in tissues treated with 5–20 mg/L PH–Mg^2 + showed no significant (P > 0.05) differences from controls at any point during the experimental period. For these reasons, PH–Fe^2 +, PH–Zn^2 +, and PH–Ca^2 + can be recommended as depuration agents in mussel feed to decrease the Cd concentrations in tissues.     

Cd(II) speciation in alginate gels

Polysaccharides, such as those occurring in cell walls and biofilms, play an important role in metal speciation in natural aqueous systems. This work describes the speciation of Cd(II) in alginate gels chosen as a model system for biogels. The gels are formed by bridging calcium ions at junction zones present along adjacent homopolymeric guluronic acid chain sequences. The free Cd2+ concentration in the gel phase is measured by a novel in situ microelectrode voltammetric technique that monitors the electroactive probe cation Cd2+ by its reduction at a Au-amalgam microelectrode. In situ voltammetric measurement coupled with total Ca(II) and Cd(II) determinations, as well as potentiometric titration, permits the full reconstruction of the charging environment and the cation binding forthe gel phase. Three independent combinations of measuring and modeling the charged gel layer thereby permit accurate prediction of the Donnan potential, psiD, and the Donnan enrichment coefficient, piD. At an ionic strength of 10 mM, Donnan potentials in the gel ranged from approximately -10 to -20 mV, corresponding to an enhancement in the level of free Cd2+ ions in the gel phase relative to the bulk solution by a factor of approximately 3. In contrast, the total level of Cd(II) was found to be enhanced by a factor of approximately 60, resulting predominantly from the specific binding of the Cd bythe uronic acids of the alginate gel. These results emphasize that large differences in Cd(II) speciation can arise due to the combination of specific and electrostatic modes of binding. The results of this speciation analysis, for charged biological gels, have important consequences for mechanistic interpretation of metal biouptake processes involved in complex media.     

Colour improvement of common carp (Cyprinus carpio) fillets by hydrogen peroxide for surimi production

The preferred colour for surimi is white, but surimi prepared from light fillets of common carp (Cyprinus carpio) is slightly pink. Hydrogen peroxide (H₂O₂; 1–3% v/v) with and without sodium tri‐polyphosphate (STP; 1–2% w/v) was added to a sodium carbonate bath (pH 7.0–11.5) resulting in a final pH range of 4.4–10.1 which was injected into carp fillets. After soaking and tumbling for 30 min at 4–10 °C, the fillets were evaluated for colour and water holding capacity (WHC). Fillets tumbled with treatment solution with different pH levels (7.0–11.5), but with no H₂O₂ or STP added, had improved colour with significantly (P < 0.05) higher L* compared with untreated fillets as the control. However, the colour improvement [(L* and colour deviation (ΔE)] was not significantly different (P > 0.05) within the pH levels (7.0–11.5) trialled. With increasing H₂O₂ levels (1–3%), fillets became lighter and ΔE increased significantly (P < 0.05), especially with a 3% H₂O₂ treatment at pH of 10.5 (adjusted pH before H₂O₂ addition, actual pH after H₂O₂ addition was 8.2). The whiteness (L*?3b*) of kamaboko produced from treated (3% H₂O₂, pH 10.5) common carp light fillets was not significantly different to that of kamaboko from Alaska pollock and threadfin bream. Treatments combining H₂O₂ (3%) with STP (1–2%) significantly reduced the L* value obtained in comparison with fillets treated with only H₂O₂ (3%). Similarly, fillets treated with STP (1%) alone, resulting in lower L* values, irrespective of treatment pH (7.0–11.5). WHC, an indicator of the quality of the fillet texture, increased from 816 g/kg at pH 7.0 without STP to 841 g/kg at pH 11.5 with 1% STP. Treatment with H₂O₂ (without STP) decreased the WHC of the fillets.     

Changes in the lipid components of minced carp (Cyprinus carpio) following cooking

The changes in weight, moisture, lipid content and composition, thiobarbituric acid (TBA) and carbonyl values were determined in minced carp following cooking by baking and deep-frying. Baked samples lost lipid via drip while the deep-fried samples absorbed oil. Free fatty acids decreased following cooking. Thiobarbituric acid (TBA) values increased following cooking by either method. Antioxidants (TBHQ and BHA) inhibited the production of TBA-reactive compounds though the production of carbonyls during deep-frying was enhanced. Tertiary butylhydroquinone (TBHQ) was slightly more effective than BHA in inhibiting the formation of TBA-reactive compounds.     

Arsenic speciation in blue mussels (Mytilus edulis) along a highly contaminated arsenic gradient

Arsenic is naturally present in marine ecosystems, and these can become contaminated from mining activities, which may be of toxicological concern to organisms that bioaccumulate the metalloid into their tissues. The toxic properties of arsenic are dependent on the chemical form in which it is found (e.g., toxic inorganic arsenicals vs nontoxic arsenobetaine), and two analytical techniques, high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) and X-ray absorption spectroscopy (XAS), were used in the present study to examine the arsenic species distribution in blue mussels (Mytilus edulis) obtained from an area where there is a strong arsenic concentration gradient as a consequence of mining impacted sediments. A strong positive correlation was observed between the concentration of inorganic arsenic species (arsenic compounds with no As-C bonds) and total arsenic concentrations present in M. edulis tissues (R(2) = 0.983), which could result in significant toxicological consequences to the mussels and higher trophic consumers. However, concentrations of organoarsenicals, dominated by arsenobetaine, remained relatively constant regardless of the increasing As concentration in M. edulis tissue (R(2) = 0.307). XANES bulk analysis and XAS two-dimensional mapping of wet M. edulis tissue revealed the presence of predominantly arsenic-sulfur compounds. The XAS mapping revealed that the As(III)-S and/or As(III) compounds were concentrated in the digestive gland. However, arsenobetaine was found in small and similar concentrations in the digestive gland as well as the surrounding tissue suggesting arsenobetaine may being used in all of the mussel's cells in a physiological function such as an intracellular osmolyte.     

Debromination of the flame retardant decabromodiphenyl ether by juvenile carp (Cyprinus carpio) following dietary exposure

The congener 2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether (BDE 209) is the primary component in a commonly used flame retardant known as decaBDE. This flame retardant constitutes approximately 80% of the world market demand for polybrominated diphenyl ethers (PBDEs). Because this compound is very hydrophobic (log K(ow) approximately 10), it has been suggested that BDE 209 has very low bioavailability, although debromination to more bioavailable metabolites has also been suggested to occur in fish tissues. In the present study, juvenile carp were exposed to BDE 209 amended food on a daily basis for 60 days, followed by a 40-day depuration period in which the fate of BDE 209 was monitored in whole fish and liver tissues separately. No net accumulation of BDE 209 was observed throughout the experiment despite an exposure concentration of 940 ng/day/fish. However, seven apparent debrominated products of BDE 209 accumulated in whole fish and liver tissues over the exposure period. These debrominated metabolites of BDE 209 were identified as penta- to octaBDEs using both GC/ECNI-MS and GC/HRMS. Using estimation methods for relative retention times of phenyl substitution patterns, we have identified possible structures for the hexa- and heptabromodiphenyl ethers identified in the carp tissues. Although exposure of carp to BDE 209 did not result in the accumulation of BDE 209 in carp tissues, our results indicate evidence of limited BDE 209 bioavailability from food in the form of lower brominated metabolites.     

A mechanistic model for the uptake of waterborne strontium in the common carp (Cyprinus carpio L.)

The release of radioactive strontium to the environment is of concern due to the strong accumulation of this calcium resembling element in the bone and other tissues. To predict the effects of changes in environmental conditions on the uptake of Sr2+ and Ca2+ by freshwater fish, a Michaelis-Menten type model is introduced that accounts for the effects of chemical speciation, hydrogen ion activity, and metal ion competition. The uptake kinetics were characterized in vivo from short-term exposure experiments using the common carp (Cyprinus carpio) as the model organism. Fish were exposed to a wide range of waterborne Sr2+ (0.2-10,000 microM) and Ca2+ (10-10,000 microM) concentrations and water pH (5.0-8.5). Strontium uptake by the whole body of fish increased with increasing Sr2+ activity, displaying saturation kinetics, but decreased significantly with increasing Ca2+ and H+ activities in the water. Likewise, calcium uptake by the fish decreased with increasing Sr2+ and H+ activities in the water. The model fitted to the pooled data explains 97.5% of the variation in Sr2+ uptake and 86% in Ca2+ uptake over the wide range of exposure conditions and reveals that Sr2+ and Ca2+ inhibit each other completely competitively, while H+ inhibits the uptake of both metal ions in a partially noncompetitive way. This model can be used as a mechanistic tool to predict the uptake of these metals in carp under variable conditions.     

Quality changes and storage life of common carp (Cyprinus carpio) at various storage temperatures

The shelf life and freshness changes in pond-grown common carp (Cyprinus carpio L) during storage at 0–2°C, 5–6°C and room temperature (26–29°C) were investigated by sensory, microbiological, physical and chemical analyses. The effect of gutting on the shelf life during storage at 0–2°C was examined. Iodine/starch and potassium sorbate were examined for their effects on shelf life of whole fish stored at 0–2°C and 5–6°C. Sensory results indicated that the whole fish had a maximum shelf life of 24 to 25 days at 0– 2°C. The life of the fish to the point beyond which it would be unsuitable for sale (commercial shelf life) was 17 days at 0–2°C. Storage at 5–6°C shortened shelf life 2- to 2.5-fold. At room temperature (26–29°C), spoilage was evident after 13 h. Gutting the carp shortened its storage potential at 0–2°C. Iodine treatment of this species stored at 0–2°C and at 5–6°C did not extend shelf life. The maximum shelf life of sorbate-treated fish at 0–2°C and 5–6°C was extended by 1–2 days, commercial shelf life by 3–4 days. Total volatile basic nitrogen, pH and penetrometer analyses were not reliable indicators of changes in freshness during shelf life. Thiobarbituric acid values were not useful as rancid odours or flavours were not detected during storage.     

Changes in functional properties of common carp (Cyprinus carpio) myofibrillar protein as affected by ultrasound-assisted freezing

Ultrasound-assisted freezing (UF) has proven to be a method that can effectively increase the freezing rate of frozen food and improve its quality. The functional properties of myofibrillar proteins (MP) are important factors that affect the further processing quality of meat products. At present, the effect of UF on the functional properties of frozen MP is not yet clear. Therefore, in the present study, changes in the functional properties (emulsifying and gel properties) of MP in common carps (Cyprinus carpio) frozen with UF at different power levels were investigated. The results revealed that, compared with immersion freezing (IF), UF at 175 W (UF-175) effectively inhibited the decrease in protein solubility, absolute Zeta potential, emulsion activity index, storage modulus (G'), and loss modulus (G'') caused by freezing. UF-175 sample had lower protein turbidity, and smaller protein particle size than any other frozen samples (P < 0.05), which suggested that UF-175 inhibited protein aggregation induced by freezing. In addition, shorter T₂₁ and T₂₂ relaxation times were obtained in UF-175 sample than other frozen samples, indicating that UF-175 reduced the mobility of immobilized and free water. Accordingly, UF-175 sample had higher gel strength and water holding capacity than other frozen samples (P < 0.05). A denser and more uniform gel network structure was also found in UF-175 sample than other frozen samples. In general, improved functional properties of common carp MP can be achieved by optimal UF.     

Ingested microscopic plastic translocates to the circulatory system of the mussel, Mytilus edulis (L)

Plastics debris is accumulating in the environment and is fragmenting into smaller pieces; as it does, the potential for ingestion by animals increases. The consequences of macroplastic debris for wildlife are well documented, however the impacts of microplastic (< 1 mm) are poorly understood. The mussel, Mytilus edulis, was used to investigate ingestion, translocation, and accumulation of this debris. Initial experiments showed that upon ingestion, microplastic accumulated in the gut. Mussels were subsequently exposed to treatments containing seawater and microplastic (3.0 or 9.6 microm). After transfer to clean conditions, microplastic was tracked in the hemolymph. Particles translocated from the gut to the circulatory system within 3 days and persisted for over 48 days. Abundance of microplastic was greatest after 12 days and declined thereafter. Smaller particles were more abundant than larger particles and our data indicate as plastic fragments into smaller particles, the potential for accumulation in the tissues of an organism increases. The short-term pulse exposure used here did not result in significant biological effects. However, plastics are exceedingly durable and so further work using a wider range of organisms, polymers, and periods of exposure will be required to establish the biological consequences of this debris.     

The inhibition mechanism of carp (Cyprinus carpio) stefin to cathepsin B and their tertiary structures

Carp is a major economic species. However, fish or surimi gel will easily soften during processing or storage due to its abundant endogenous protease, which will seriously affect the product quality. Because of the high inhibitory activity to cysteine protease, stefin has great potential as an additive for the improvement of fish softening. In this study, molecular dynamics simulation was used to explore the inhibition mechanism of carp stefin to cathepsin B (CTS B) and their tertiary structures. The results showed that carp stefin is a single domain protein with four stranded β-sheets and a α-helix. CTS B is a typical papain-like fold containing two domains. During the inhibition process, the wedge-shaped structure created by N-terminal trunk and the two hairpin loops of stefin would insert into the groove between two domains of CTS B. Besides, the inhibition can be spontaneous in pure water through hydrogen bonding, VDW and electrostatic interactions. And the Cys3, His83 and Val49 of carp stefin were the critical residues for the inhibition to CTS B. The results may provide a theoretical reference for the application of stefin in the processing and storage of fish products.     

Biogenic amines in vacuum-packed and non-vacuum-packed flesh of carp (Cyprinus carpio) stored at different temperatures

Samples of carp flesh (Cyprinus carpio), vacuum-and non-vacuum-packed were stored at 3 and 15 °C. Chemical, sensory and microbial qualities were measured throughout the storage time to determine the changes that took place and to evaluate the effects of both storage temperature and the means of packaging. Seven biogenic amines (putrescine, cadaverine, spermidine, spermine, histamine, tyramine and tryptamine) were determined. Putrescine and cadaverine showed the best correspondence with the sensory and microbial states of the samples. Low storage temperature had a dominant effect, resulting in low biogenic amine content and better quality of samples. The effect of vacuum-packaging was less obvious, especially in samples kept at 15 °C. Application of vacuum-packaging at 3 °C prolonged the shelf life by about 4–5 days.