Treatment of textile effluents with Pistia stratiotes,Eichhornia crassipes and Oedogonium sp.

Abstract

Phytoremediation by aquatic macrophytes is a promising technology with higher efficiency and no energy consumption. For this purpose, two macrophytes (Pistia stratiotes, Eichhornia crassipes), and an alga (Oedogonium sp.) were used to treat textile effluents rich in COD, BOD, dyes, and heavy metals (Pb, Fe, Cd, Cu). The aim of the study was to focus on comparative phytoremediation potential of these species by their metal removal capability. During 7?days experiment (day 0–day 6), the results showed that Oedogonium sp. was the best for COD removal and decolorization. Eichhornia crassipes was the best for BOD and heavy metal removal and proves more efficient than Pistia stratiotes and Oedogonium sp. However, Pistia stratiotes was found to accumulate more concentrations of Pb and Fe than Eichhornia stratiotes.     

Interaction of Heavy Metals in Multimetal Biosorption by Galerina vittiformis from Soil

ABSTRACT Soil heavy metal contamination, a major threat due to industrialization, can be tackled by an efficient and economical process called bioremediation. Mushrooms are employed to accumulate heavy metals from soil due to their high metal accumulation potential and better adaptability. The bioaccumulation potential of Galerina vittiformis was already reported for individual metals. At natural conditions, since soil consists of more than one polluting metal, more focus has to be given to multimetal systems. In this study, multimetal accumulation potential was analyzed using central composite design, and the responses obtained were analyzed using response surface methodology. Heavy metals such as Cu(II), Cd(II), Cr(VI), Pb(II), and Zn(II) were subjected to biosorption at 10–250 mg/kg concentrations along with pH 5–8. The results showed that the preference of the organism for the five metals under study was in the order Pb(II) > Zn(II) > Cd(II) > Cu(II) > Cr(VI) at pH 6.5 under multimetal condition. The study also indicates that the metal interaction pattern in multimetal interaction is a property of their ionic radii. The response surface methodology clearly explains the effect of interaction of heavy metals on the accumulation potential of the organism using three-dimensional response plots. The present work suggests that the fungus Galerina vittiformis could be employed as a low-cost metal removal agent from heavy metal–polluted soil.     

Decontamination of coal mine effluent generated at the Rajrappa coal mine using phytoremediation technology

Toxicity of the effluent generated at the Rajrappa coal mine complex under the Central Coalfields Limited (CCL, a subsidiary of Coal India Limited) in Jharkhand, India was investigated. The concentrations (mg L^?1) of all the toxic metals (Fe, Mn, Ni, Zn, Cu, Pb, Cr, and Cd) in the coal mine effluent were above the safe limit suggested by the Environmental Protection Agency (EPA 2003). Among these, Fe showed the highest concentration (18.21 ± 3.865), while Cr had the lowest effluent concentration (0.15 ± 0.014). Efforts were also made to detoxify the effluent using two species of aquatic macrophytes namely “‘Salvinia molesta and Pistia stratiotes.” After 10 days of phytoremediation, S. molesta removed Pb (96.96%) > Ni (97.01%) > Cu (96.77%) > Zn (96.38%) > Mn (96.22%) > Fe (94.12%) > Cr (92.85%) > Cd (80.99%), and P. stratiotes removed Pb (96.21%) > Fe (94.34%) > Ni (92.53%) > Mn (85.24%) > Zn (79.51%) > Cr (78.57%) > Cu (74.19%) > Cd (72.72%). The impact of coal mine exposure on chlorophyll content showed a significant decrease of 42.49% and 24.54% from control values in S. molesta and P. stratiotes, respectively, perhaps due to the damage inflicted by the toxic metals, leading to the decay of plant tissues.     

Phytoextraction of Ni,Pb and,Cd by duckweeds

Abstract

Heavy metals phytoextraction potential of swollen duckweed (Lemna gibba Linn.) and lesser duckweed (Lemna aequinoctialis Welw.) was determined under greenhouse conditions by exposing to untreated industrial/municipal effluent for a period of 21?days. The nickel (Ni), lead (Pb), and cadmium (Cd) concentrations in water samples were measured weekly and in plant biomass at the termination of experiments. Significant differences (p?<?0.05) between initial and final physicochemical parameters and in heavy metal concentrations of plant and water samples were observed. Periodically measured metal concentrations in mediums revealed that removal percentage was dependent on initial Ni (2.15?mg L^?1), Pb (1.51?mg L^?1), and Cd (0.74?mg L^?1) concentrations. The final metal removal percentages were in the sequence of Ni (97%) > Pb (94%) > Cd (90%) when treated with Lemna gibba L. as compared to control (9–12% reduction). High biomass production of Lemna gibba L. resulted in a large metal reduction in the growth medium and the total plant metal contents were in the sequence of Ni (427?µg) > Pb (293?µg) > Cd (105?µg). The lesser duckweed did not survive under experimental conditions. Based on these results, we concluded that Lemna gibba L. is a good candidate for phytoremediation of wastewater.     

The species composition,occurrence and temporal stability of submerged aquatic macrophyte patches along the main channel border of pool 5A,Upper Mississippi River

Species composition, relative abundance, distribution and physical habitat associations of submerged aquatic macrophytes in the main channel border (MCB) habitat of Pool 5A, Upper Mississippi River (UMR) were investigated during the summers of 1980 and 1983. The submerged aquatic macrophytes in Pool .5A MCB were a small and stable component of the river ecosystem. Submerged plants occurred primarily in small, monospecific clumps. Clumps in close proximity to each other formed plant patches. Plant patches were stable in location and number between 1980 and 1983; 82.5% of the patches first observed in 1980 were present in 1983. Submerged macrophytes covered about 10–12 ha of the 201 ha MCB in Pool 5A. Submerged plants were most common in the lower two-thirds of the pool. Ten species of aquatic macrophytes occurred on rock channel-training structures and eleven occurred on non-rock substrates in the MCB. The most common submerged plants, in order of abundance, were Vallisneria americana Michx., Heteranthra dubia Jacq., Potamogeton pectinatus L., Ceratophyllum demersum L. and Potamogeton americanus C. & S.     

Status of Selected Heavy Metal Distribution in Scalp Hair of Traffic Control Personnel Exposed to Vehicular Emissions

Scalp hair samples of traffic control personnel (n = 71, ages between 25 to 45 years) were analyzed for 11 selected metals by using an Inductively Coupled Argon Plasma Atomic Emission (ICP-AE) technique using nitric acid–perchloric acid based wet digestion method. The observed order of mean concentrations (μ g/g, dry weight) of the metals, in washed hair samples, was: Ca > Mg > Zn > Fe > Pb > Cu > Ni > Mn > Cr > Cd > Co, with corresponding metal levels at 1042.2, 182.4, 169.7, 13.6, 12.4, 11.1, 2.7, 1.9, 1.9, 0.8, and 0.7 μ g/g, respectively. Most of the unwashed samples exhibited 10–15% higher metal levels compared with those in washed samples. A positive metal-to-metal correlation (p < 0.01) was observed for the metal pairs: Ca-Mg (r = 0.737), Pb-Cr (r = 0.441), and Cu-Zn (0.385). Principal Component Analysis (PCA) extracted 6 factors as metals origin using varimax normalized rotation commutatively representing more than 76% of the total variance. Cluster Analysis (CA) showed five strong clusters of selected metals in the hair of the subjects: Age-Exposure, Ca-Mg, Cd-Fe-Mn, Pb-Cr, and Cu-Zn. The results of the current study were compared with those for two other occupationally exposed groups, metal arc welders and autodrivers, using published literature values. The traffic controllers in our study generally, with the exception of Cu, exhibited lower levels of metals in hair samples than did autodrivers and arc welders.     

Application of phytoremediation technology in decontamination of a fish culture pond fed with coal mine effluent using three aquatic macrophytes

Abstract

In the present study, three aquatic macrophytes, Eichhornia crassipes, Salvinia molesta, and Pistia stratiotes were used to assess their relative efficacies in decontamination of a fish culture pond, regularly fed with coal mine effluent (CME). The level of metals like Fe, Mn, Ni, Zn, Cu, Pb, Cr, and Cd were much higher in CME-fed pond water than their recommended limits in drinking water set by the Bureau of Indian standards and in effluents by the Environmental Protection Agency. The levels of metal were lowered substantially in CME-fed pond water after exposure of the above plants to such water, however, metal levels in the plants increased tremendously. The increased metal levels in plants severely damaged their physiological and biochemical processes. The contents of chlorophyll a, b and carotenoid were reduced by 63.2, 64.2, and 46.3%, respectively, in E. crassipes, 41, 57.4, and 57.8% in S. molesta, and 42, 62, and 61% in P. stratiotes. The accumulating metals also generated oxidative stress in plants, as evident from the increased superoxide dismutase and catalase activities and enhanced malondialdehyde content. The E. crassipes was the most potent in absorbing the metals from the CME-fed pond water, followed by S. molesta and P. stratiotes.     

Solid state fermentation of aquatic macrophytes for crude protein extraction

Aquatic macrophytes such as Elodea nuttalli, Vallisneria natans, Alterranthera philoxerides that are widely distributed in water environments of Lake Taihu basin were used as substrate of solid state fermentation to produce crude protein extraction. The effects of single-strain fermentation and mixed strains fermentation of aquatic macrophytes on the production of crude protein extraction and cellulase activity are analyzed, respectively. The experimental results showed that the crude protein content of products with mixed strains fermentation is higher than that with single-strain fermentation. The crude protein content of V. natans fermented by Aspergillus niger and Candida utilis is the highest among the aquatic macrophytes examined in this study. V. natans is used as the substrate to be fermented by C. utilis and A. niger; their ratio is 1:1 at 28 ± 1 °C for 72 h. The crude protein of fermented V. natans is as high as 49.54%, with 128.82% of its increase rate. The cellulose activity reaches a maximum of 4.21 μ/ml at 84 h of fementation of V. natans. Thus, the solid state fermentation of aquatic macrophytes to produce crude protein extraction is promising, which make aquatic macrophytes a potential resource and thus is beneficial to the long-term ecological restoration of eutrophic lakes.     

Phytoremediation of landfill leachate waste contaminants through floating bed technique using water hyacinth and water lettuce

Abstract

In the present study, the effectiveness of water hyacinth and water lettuce was tested for the phytoremediation of landfill leachate for the period of 15?days. Fifteen plastic containers were used in experimental setup where aquatic plants were fitted as a floating bed with the help of thermo-pole sheet. It was observed that both plants significantly (p?<?0.05/p?<?0.01/p?<?0.001) reduce the physicochemical parameters pH, TDS, BOD, COD and heavy metals like Zn, Pb, Fe, Cu and Ni from landfill leachate. Maximum reduction in these parameters was obtained at 50% and 75% landfill leachate treatment and their removal rate gradually increased from day 3 to day 15 of the experiment. The maximum removal rate for heavy metals such as for Zn (80–90%), Fe (83–87%) and Pb (76–84%) was attained by Eichhornia crassipes and Pistia stratiotes. Value of bioconcentration and translocation factor was less than 1 which indicates the low transport of heavy metals from roots to the above-ground parts of the plants. Both these plants accumulate heavy metals inside their body without showing much reduction in growth and showing tolerance to all the present metals. Therefore, results obtained from the study suggest that these aquatic plants are suitable candidate for the removal of pollution load from landfill leachate.     

Biosorption of Heavy Metals from Wastewater by Biosolids

In a study where the removal of heavy metals from wastewater is the primary aim, the biosorption of heavy metals onto biosolids prepared as Pseudomonas aeruginosa immobilized onto granular activated carbon was investigated in batch and column systems. In the batch system, adsorption equilibriums of heavy metals were reached between 20 and 50 min, and the optimal dosage of biosolids was 0.3 g/L. The biosorption efficiencies were 84, 80, 79, 59 and 42 % for Cr(VI), Ni(II), Cu(II), Zn(II) and Cd(II) ions, respectively. The rate constants of biosorption and pore diffusion of heavy metals were 0.013–0.089 min^–1 and 0.026–0.690 min^–0.5. In the column systems, the biosorption efficiencies for all heavy metals increased up to 81–100 %. The affinity of biosorption for various metal ions towards biosolids was decreased in the order: Cr = Ni > Cu > Zn > Cd.     

Mercury Pollution from a Chloralkali Source in a Tropical Lake and Its Biomagnification in Aquatic Biota: Link between Chemical Pollution,Biomarkers, and Human Health Concern

Mercury is a highly toxic heavy metal that can cause adverse ecological and toxicological impacts through the mechanism of biomagnification. Hg accumulation in aquatic biota may thus also pose a serious threat to humans and other fish-eating animals. The present work observed the transfer of Hg from abiotic (water and sediments) to biotic (algae, aquatic macrophytes, and fish) components, belonging to different trophic levels in a tropical lake in India. Hg was analyzed in water, sediments, plants, and fish collected from different sampling points, receiving the discharge of chloralkali effluent. Hg concentrations increased significantly from lake water and sediments to algae and aquatic macrophytes. Statistical analysis (Pearson correlation) revealed a significant positive correlation between Hg in water and plants (r = 0.88–0.93; p < .01 and p < .05) as well as for Hg in sediment and plants (r = 0.50–0.83; p < .01 and p < .05). However, the increase in Hg concentration in fish was not significantly correlated with lake ambient water (r = 0.31–0.36), sediments (r = 0.29–0.33), and aquatic plants (r = 0.31–0.36). Results obtained encourage the use of naturally occurring wetland plants in designed systems like constructed wetlands to ameliorate Hg pollution in lakes, rivers, and ponds resulting from the discharge of industrial effluents, especially chloralkali effluent, hence reducing the human health risks associated with Hg.     

Heavy metals contamination and accumulation in submerged macrophytes in an urban river in China

Deteriorating urban water quality has attracted considerable attention in China. We investigated the contamination levels and distribution of heavy metals (As, Cd, Cu, Ni, Pb, and Zn) in Yuxi River water and sediments, and assessed the heavy metal accumulation capability of five species of submerged macrophytes: Vallisneria natans (Lour.) Hara, Potamogeton pectinatus L., Hydrilla verticillata (L. f.) Royle, Myriophyllum spicatum L., and Potamogeton crispus L. Samples were collected from upstream and downstream locations in different season. The results showed that the levels of heavy metals in the downstream areas were higher than in the upstream areas. Heavy metal concentrations in the river water during the dry seasons were higher than those during the rainy seasons, and the opposite results appeared in sediments and submerged macrophytes. In general, the river was slightly contaminated by heavy metals, and the concentrations of Pb and Ni in this river should serve as a warning, while Cd and Zn pollution in the sediments desperately needs to be removed. Furthermore, Potamogeton pectinatus L. showed a higher accumulation capacity for these metals among the five native submerged macrophytes and could be defined as a hyperaccumulator for Cd. Therefore, the potential use of native aquatic plants in contaminated rivers is worth further exploration.     

Trace elements removal ability and antioxidant activity of Phragmites australis (from Algeria)

Abstract

In this study, roots, stems and leaves of the worldwide distributed macrophyte Phragmites australis (common reed) were tested as potential removal and biomonitors of trace elements contamination in sediment. In particular, the concentrations (100, 200, and 500?mg/kg) of the following elements were analyzed: Zn, Cu, Pb, and Fe. Results showed that the amount of concentrations in plant tissues is significantly (p?≤?0.01) dependent on the kind of organ and element. Trace element concentrations decreased according to the pattern of Fe^a (Roots^a > Stems^b > Leaves^b) > Zn^b (Root^a > Leaves^b > Stems^c) > Cu^c (Roots^a > Leaves^b > Stems^c) > Pb^c (Roots^a > Stems^b > Leaves^c), as well as the roots acted as the main centers of bioaccumulation for all elements studied, and stems as the transit organs for translocation from roots to leaves. The major mechanisms employed by the plant were probably phytostabilization on the basis of the calculated Biological Concentration Factor (BCF – metal concentration ratio of plant root to soil); and Translocation Factor (TF – metal concentration ratio of plants roots to above ground part). Finally, due to the low scavenger effect of the radical DPPH, we excluded the hypothesis of the use of antioxidant mechanism in the tolerance of metals.     

Bioaccumulation of Trace Elements in Trophic Levels of Wetland Plants and Waterfowl Birds

Present study investigates relationships between total and bioaccessibility of trace elements (Cd, Co, Cr, Cu, Mn, NI, Pb, V, and Zn) concentrations in sediment and their bioaccumulation in species in Shadegan wetland in southwest of Iran. Bioavailability factor (BAF) and translocation factor (TF) were calculated in plants and trophic transfer factor (TTF) was determined in bird species. For this purpose, sampling of sediments, aquatic plants including Phragmites australis, Typha australis, Scripus maritimus and two bird species encircling Porphyrio porphyrio and globally threatened Marmaronetta angustirostris were carried out during winter 2009. Result of chemical analysis show that bioaccessibility concentrations of Mn (8.31 mg/kg), V (1.33 mg/kg), and Pb (1.03 mg/kg) are higher than other metals. The uptake trend of trace elements in plant decreases as root > stem > leaf. Accumulation levels of trace elements in different tissues of P. porphyrio and M. angustirostris are almost identical and considerable. Accumulation and toxicity of Cd in birds is more than plants. In addition, BAF of V, Pb, and Cr indicates high accumulation by plants and great pollution rate in the area of study. In S. maritimus TF for Mn, Cu, Pb, and V are high whereas in T. australis, Cu and Pb posses the highest TF. Also Cr, Co, Mn, Ni, and Zn have higher TF from stem to leaf than root to stem in P. australis. Finally, TTFs were compared in various bird species.     

AQUATIC MACROPHYTE COMMUNITIES OF THE WILDERNESS LAKES: COMMUNITY STRUCTURE AND ASSOCIATED ENVIRONMENTAL CONDITIONS

SUMMARY

The structure and summer biomass (g m^?2 dry mass) of the principal aquatic macrophyte communities of the Wilderness Lakes were measured. Both emergent and submerged communities were included in the study. Productivity estimates were made by multiplying biomass by production/biomass ratios for each species. Salinity gradients in the system are described and details of the different sediment types associated with the macrophytes are given. There was considerable variation in production rates between the different water bodies often coinciding with a salinity gradient. However, rapid, natural changes in the communities are described which also influence production rates in a given water body. Production rates (g dry mass m^?2 a^?1) were of the order: Typha latifolia > Phragmites australis > Scirpus littoralis > Potamogeton pectinatus > Chara qlobularis > Ruppia cirrhosa. The significance of the macrophyte rates is discussed in relation to Wilderness Lakes area as a whole.     

Jasmonic acid as modulator of lead toxicity in aquatic plant Wolffia arrhiza (Lemnaceae)

The present study was undertaken to test the influence of exogenously applied jasmonic acid (JA) upon the growth and metabolism of Wolffia arrhiza (Lemnaceae), the smallest vessel aquatic plant exposed to lead (Pb) stress. It was found, that JA acted in a concentration-dependent manner. Treatment with JA at the highest concentration 100 μM resulted in the enhancement of heavy metal toxicity leading to increase in metal biosorption and formation of lipid peroxides as well as decrease in fresh weight, chlorophyll a, carotenoid, monosaccharide and soluble protein content. In contrast, this phytohormone applied at 0.1 μM protected W. arrhiza fronds against Pb stress inhibiting heavy metal accumulation, restoring plant growth and primary metabolite level. Moreover, JA at 0.1 μM activated enzymatic (catalase, ascorbate peroxidase, NADH peroxidase) and non-enzymatic antioxidant (ascorbate, glutathione) system in W. arrhiza, and therefore, suppressed oxidative destruction of cellular components induced by heavy metal. The data suggest that JA plays an important role in the growth and metabolism of W. arrhiza exposed to abiotic stressor and its high adaptation ability to metal contamination of aquatic environment.     

Fate of heavy metals in vertical subsurface flow constructed wetlands treating secondary treated petroleum refinery wastewater in Kaduna,Nigeria

This study examined the performance of pilot-scale vertical subsurface flow constructed wetlands (VSF–CWs) planted with three indigenous plants, i.e. Typha latifolia, Cyperus alternifolius, and Cynodon dactylon, in removing heavy metals from secondary treated refinery wastewater under tropical conditions. The T. latifolia-planted VSF–CW had the best heavy metal removal performance, followed by the Cyperus alternifolius-planted VSF–CW and then the Cynodon dactylon-planted VSF–CW. The data indicated that Cu, Cr, Zn, Pb, Cd, and Fe were accumulated in the plants at all the three VSF–CWs. However, the accumulation of the heavy metals in the plants accounted for only a rather small fraction (0.09–16%) of the overall heavy metal removal by the wetlands. The plant roots accumulated the highest amount of heavy metals, followed by the leaves, and then the stem. Cr and Fe were mainly retained in the roots of T. latifolia, Cyperus alternifolius, and Cynodon dactylon (TF < 1), meaning that Cr and Fe were only partially transported to the leaves of these plants. This study showed that VSF–CWs planted with T. latifolia, Cyperus Alternifolius, and Cynodon dactylon can be used for the large-scale removal of heavy metals from secondary refinery wastewater.     

The quality of the aquatic environment and macrophytes of karstic watercourses

The quality of the aquatic environment and macrophytes were surveyed in the case of the remarkable karstic river Ljubljanica s. lat. (Slovenia). It consists of seven intermittent and permanent surface watercourses, connected by groundwater flows. We assessed 11 parameters describing the land use beyond the riparian zone, the structure of the riparian zone and stream channel morphology, as well as the distribution and abundance of macrophytes. The intermittent watercourses exhibited a relatively high level of naturalness, because the variable water regime prevents intensive human activity. Greater influence of the human activity on the permanent watercourses resulted in a modified riverine environment. The share of different ecological groups of macrophytes, i.e. submerged, emerged and amphibious species, reflected the water regimes of the different watercourses. A total of 62 taxa of macrophytes were identified in about 100 km of length examined. Of these, amphibious macrophytes dominated as a consequence of intermittent water regime. The relationship between environmental parameters and macrophytes, and the effects of the intermittent hydrology were investigated. All environmental parameters explained 28% of the variance in the distribution of macrophytes in watercourses, as determined by canonical correspondence analysis. Completeness of the riparian zone, bank undercutting and sediment accumulation were found to be the most influential.     

The Development of a Phytoremediation Technique for the Detoxification of Soils Contaminated with Phenolic Compounds Using Horseradish Peroxidase (Armoracia rusticana): Preliminary Results

The proposed phytoremediation technique is based on the successful exploitation and optimization of oxidative coupling, mediated by horseradish peroxidase. Susceptibility to degradation of a selection of phenolic compounds, in solution, by horseradish peroxidase appears to be structurally related and was found to be of the order 2,4-dichlorophenol (2,4-DCP) > 4-chlorophenol (4-CP) > 2-chlorophenol (2-CP). Only 1.89% of 2,4-DCP, at an initial concentration of 5 mM, remained unchanged at the end of the experiment. Reaction rates between purified horseradish peroxidase and 2,4-DCP were found to be extremely rapid with 74% of the substrate removed from solution during the first 30 s. Inhibition of the reaction by the heavy metals Cd, Zn, Ni, and Pb at concentrations of 100 mg/l is of concern because these metals are often present in contaminated soils. H₂O₂ has a dominant role in optimizing peroxidase activity in crude horseradish extracts. Fluctuations in temperature and pH, normally experienced in soils, did not appear to have a detrimental impact on peroxidase activity. However, the functioning of the enzyme is seriously affected at a pH ≤ 3. All reactions in this study were carried out in solution.     

Metal dependent hydrolysis of β‐casein by sIgA antibodies from human milk

We present the first evidence that electrophoretically and immunologically homogeneous sIgAs purified from milk of healthy human mothers by chromatography on Protein A‐Sepharose and FPLC gel filtration contain intrinsically bound metal ions (Ca > Mg ≥ Al > Fe ≈ Zn ≥ Ni ≥ Cu ≥ Mn), the removal of which by a dialysis against ethylenediamine tetraacetic acid (EDTA) leads to a significant decrease in the β‐casein‐hydrolyzing activity of these antibodies (Abs). An affinity chromatography of total sIgAs on benzamidine‐Sepharose interacting with canonical serine proteases separates a small metalloprotease sIgA fraction (6.8 ± 2.4%) from the main part of these Abs with a serine protease‐like β‐casein‐hydrolyzing activity. The relative activity of this metalloprotease sIgA fraction containing intrinsically bound metal ions increases ～1.2–1.9‐fold after addition of external metal ions (Mg²⁺ > Fe²⁺ > Cu²⁺ ≥ Ca²⁺ ≥ Mn²⁺) but decreases by 85 ± 7% after the removal of the intrinsically bound metals. The metalloprotease sIgA fraction free of intrinsic metal ions demonstrates a high β‐casein‐hydrolyzing activity in the presence of individual external metal ions (Fe²⁺ > Ca²⁺ > Co²⁺ ≥ Ni²⁺) and especially several combinations of metals: Co²⁺ + Ca²⁺ < Mg²⁺ + Ca²⁺ < Ca²⁺ + Zn²⁺ < Fe²⁺ + Zn²⁺ < Fe²⁺ + Co²⁺ < Fe²⁺ + Ca²⁺. The patterns of hydrolysis of a 22‐mer oligopeptide corresponding to one of sIgA‐dependent specific cleavage sites in β‐casein depend significantly on the metal used. Metal‐dependent sIgAs demonstrate an extreme diversity in their affinity for casein‐Sepharose and chelating Sepharose, and interact with Sepharoses bearing immobilized monoclonal mouse IgGs against λ‐ and κ‐type light chains of human Abs. Possible ways of the production of metalloprotease abzymes (Abz) by human immune system are discussed. Copyright © 2010 John Wiley & Sons, Ltd.