Lethal critical body residues as measures of Cd,Pb, and Zn bioavailability and toxicity in the earthworm<Emphasis Type="Italic">Eisenia fetida</Emphasis>

Background

Earthworm heavy metal concentrations (critical body residues, CBRs) may be the most relevant measures of heavy metal bioavailability in soils and may be linkable to toxic effects in order to better assess soil ecotoxicity. However, as earthworms possess physiological mechanisms to secrete and/or sequester absorbed metals as toxicologically inactive forms, total earthworm metal concentrations may not relate well with toxicity.

Objective

The objectives of this research were to: i) develop LD₅₀s (total earthworm metal concentration associated with 50% mortality) for Cd, Pb, and Zn; ii) evaluate the LD₅₀ for Zn in a lethal Zn-smelter soil; iii) evaluate the lethal mixture toxicity of Cd, Pb, and Zn using earthworm metal concentrations and the toxic unit (TU) approach; and iv) evaluate total and fractionated earthworm concentrations as indicators of sublethal exposure.

Methods

Earthworms (Eisenia fetida (Savigny)) were exposed to artificial soils spiked with Cd, Pb, Zn, and a Cd?Pb?Zn equitoxic mixture to estimate lethal CBRs and mixture toxicity. To evaluate the CBR developed for Zn, earthworms were also exposed to Zn-contaminated field soils receiving three different remediation treatments. Earthworm metal concentrations were measured using a procedure devised to isolate toxicologically active metal burdens via separation into cytosolic and pellet fractions.

Results and Discussion

Lethal CBRs inducing 50% mortality (LD₅₀, 95% CI) were calculated to be 5.72 (3.54–7.91), 3.33 (2.97–3.69), and 8.19 (4.78–11.6) mmol/kg for Cd, Pb, and Zn, respectively. Zn concentrations of dead earthworms exposed to a lethal remediated Zn-smelter soil were 3-fold above the LD₅₀ for Zn and comparable to earthworm concentrations in lethal Zn-spiked artificial soils, despite a 14-fold difference in total soil Zn concentration between lethal field and artificial soils. An evaluation of the acute mixture toxicity of Cd, Pb, and Zn in artificial soils using the Toxic Unit (TU) approach revealed an LD₅₀ (95% CI) of 0.99 (0.57–1.41) TU, indicating additive toxicity.

Conclusions

Total Cd, Pb, and Zn concentrations in earthworms were good indicators of lethal metal exposure, and enabled the calculation of LD₅₀s for lethality. The Zn-LD₅₀ developed in artificial soil was applicable to earthworms exposed to remediated Zn-smelter soil, despite a 14-fold difference in total soil Zn concentrations. Mixture toxicity evaluated using LD₅₀s from each single metal test indicated additive mixture toxicity among Cd, Pb, and Zn. Fractionation of earthworm tissues into cytosolic and pellet digesis yielded mixed results for detecting differences in exposure at the sublethal level.

Recommendation and Outlook

CBRs are useful in describing acute Cd, Pb, and Zn toxicity in earthworms, but linking sublethal exposure to total and/or fractionated residues may be more difficult. More research on detoxification, regulation, and tissue and subcellular partitioning of heavy metals in earthworms and other invertebrates is needed to establish the link between body residue and sublethal exposure and toxicity.

     

Synthesis of Molecular Imprinting Polymers Separating Toluic Acid Isomers (II)

Polymers that can separate toluic acid isomers were synthesized by molecular imprinting technique. Molecular imprinting polymers (MIPs) for each isomer of toluic acids (TA) were synthesized using styrene and 4-vinylpyridine (4-Vpy). The adsorption characteristics of TA isomers, salicylic acid (SA), and benzoic acid (BA) on each MIP were investigated. The materials used for polymerization of TA isomers MIPs were adsorbed relatively well. This verifies that the MIPs which can adsorb template selectively were synthesized. In addition, the quantities of adsorbed TA isomers on the TA isomers MIPs and on the control polymer polymerized without template were compared and discussed. The variation of adsorption ability for MIPs with repeated use was investigated, showing excellent reproducibility.     

Sustainable Cellular Biocomposites from Natural Fibers and Unsaturated Polyester Resin for Housing Panel Applications

Increased environmental awareness and interest in long-term sustainability of material resources has motivated considerable advancements in composite materials made from natural fibers and resins, or biocomposites. In spite of these developments the lower stiffness and strength of biocomposites has limited their applications to non-load-bearing components. This paper presents an overview of a study aimed at showing that the shortcomings of biocomposites can be overcome through hybrid material designs and efficient structural configurations to make them suitable for load bearing structural components. Hybrid blends of natural and synthetic fibers can significantly improve the characteristics of biocomposites with minimal cost and environmental impact, and hierarchical cellular designs can maximize material efficiency in structural components. Periodic and hierarchical cellular plate designs made from natural fibers and unsaturated polyester resin were evaluated experimentally and analytically. Stiffness, strength, and dimensional stability of all-biocomposite and hybrid natural–synthetic material systems were evaluated through material tests while structural performance of cellular plate designs was assessed through flexural tests on laboratory-scale samples. The experimental results were correlated with analytical models for short-fiber composites and cellular structures. The results showed that biocomposites have adequate short-term performance and that they can efficiently compete with housing panels made from conventional structural materials.     

Preliminary Studies on Converting Agricultural Waste into Biodegradable Plastics—Part IV: Polysaccharide Containing Natural Materials

Corn distillers’ dry grain, corncob powder, hardwood powder, and sugar beet pulp were separately anionized by oxidation with sodium hypochlorite in aqueous solution. Solid reaction products instantly precipitated upon admixing each of the above-oxidized materials with soy protein isolate. Infrared spectra and differential scanning calorimetry supported the hypothesis that soy protein isolate complexed with all of the above-oxidized polysaccharides. Reaction products with either oxidized corn distillers’ dry grain or oxidized sugar beet pulp provided hard, brittle pellets with tensile strengths as high as 9.5 MPa, suggesting that these materials could be viable as biodegradable plastics.     

Role of Amino Acids on <Emphasis Type="Italic">In Situ</Emphasis> Photografting of Jute Yarn with 3-(Trimethoxysilyl) Propylmethacrylate

To improve the mechanical performance of natural lignocellulosic jute yarn, grafting with [3-(trimethoxysilyl) propylmethacrylate] (TMSPM) monomer has been performed on in situ UV radiation and optimized the monomer concentration (30%) and irradiation time (30 min). Effect of various amino acids (1%) as additives in TMSPM with photografted jute yarn at optimized system has been studied. The polymer loading (PL) and tensile properties like tensile strength (TS) and elongation at break (Eb) of treated samples were enhanced by incorporation of amino acids and the highest properties (TS = 300% and Eb = 386%) achieved by the sample treated with l-Arginine (Arg) with 32.5% PL value. Weak acid like 3% acetic acid and inorganic acid like 1% sulfuric acid were also incorporated in the optimized system of TMSPM grafting and compared their effect on the tensile properties with amino acid treated samples. Water absorption and weathering resistance of treated and untreated samples were also performed and treated sample showed lesser water uptake as well as less weight loss and mechanical properties as compared to untreated samples.     

Leachability testing of metallic wastes.

The performance of two tests, a batch test and a percolation test for the characterization of waste as suggested in the EU council decision 2003/33/EC was investigated. The tests were carried out on two solid waste streams from a metal recycling industry. The concentrations of heavy metals such as Cu, Zn and Pb were more than one order of magnitude lower than the proposed limit values. Generally, batch test values were equal or higher than percolation test values. With the proposed test procedures both materials could be considered as non-dangerous wastes. The test performance was also investigated using a leachant with higher ionic strength instead of demineralized water as prescribed. The results clearly show a significant increase in the concentration of some heavy metals. Total concentrations of phenolic compounds and polychlorinated biphenyls were less than 1 p.p.m. and 2 p.p.b., respectively. The precision of the batch and the percolation tests were on average 48 and 35%, respectively.     

Static and Dynamic Behavior of Fibrous Polymeric Composite Materials at Different Environmental Conditions

The study of static and dynamic behavior of environmentally conditioned fibre reinforced polymeric (FRP) composites is necessary and crucial to examine the durability, reliability and sustainability of these noble materials. FRP composites are being used all around the globe and substituting the conventional materials, starting from mini toys to large aerospace components. Present review has introduced to accumulate and understand the disseminate literature in concentrating the significance of understanding the static and dynamic behavior of FRPs with changing environmental conditionings (hygrothermal, low and high temperature, salt solution, freeze thaw, UV light) and with the interaction of different nano-fillers. Their stability and integrity in diverse service environments may be reformed by their reactions against different nature of loadings i.e. static or dynamic and the components such as fibre, matrix and fibre/matrix interfaces in those environments. The static and dynamic states of loading may come with a possible weaker region to encounter the durability and integrity of the composites. To understand the exact failure modes that correlates the position of environmentally conditioned interfaces and dynamic state of loadings, thus confusing the estimation of its overall performance and mechanical behavior. Interface reliability and durability is vital since in-service environments the degradation in the interfacial region leads to complete composite failure. Therefore, the study of combined effects of various in-service environmental conditions and the role of static and dynamic behavior on the interface will be a crucial part related to the multiaxial dynamic states of failures occurring in FRP’s.     

The Effect of CTBN Concentrations on the Kinetic Parameters of Decomposition of Blends of Epoxy Resins Modified with Carboxyl-Terminated Liquid Copolymer

Diglycidyl ether of bisphenol—A (DGEBA)—based epoxy resin was blended in the ratio of 3:1 (weight basis) with cycloaliphatic epoxy (CAE) resin. The prepared blend sample was further blended with different weight percentages of carboxyl-terminated butadiene acrylonitrile copolymer (CTBN) ranging between 0 and 25 wt% with an interval of 5 wt% and cured with stiochiometric amounts of 4, 4’- diamino diphenyl sulphone (DDS) cure agent. Structural changes during blending were studied by Fourier-transform infra-red (FTIR) spectroscopic analysis. The kinetic parameters, viz., order of decomposition reaction (n), activation energy (E), pre-exponential factor (Z) and rate decomposition constant (k), for the decomposition of the samples were calculated by applying Coats-Redfern equation over thermogravimetric (TG) data. The degradation of each sample followed second-order degradation kinetics, which was calculated by Coats-Redfern equation using best-fit analysis. This was further confirmed by linear regression analysis. The validity of data was checked by t-test statistical analysis. Further, the blend sample had higher initial degradation temperature and activation energy than its respective pure epoxy resin indicating that the CTBN acted as thermal stabilizer for epoxy resin which improved the thermal stability.