Invertebrates control metal/metalloid sequestration and the quality of DOC/DON released during litter decay in slightly acidic environments

Plant litter and organic sediments are a main sink for metals and metalloids in aquatic ecosystems. The effect of invertebrate shredder (a key species in litter decay) on metal/metalloid fixation by organic matter is described only under alkaline water conditions whereas for slightly acidic waters nothing can be found. Furthermore, less is known about the effect of invertebrate shredders on the quality of dissolved organic carbon (DOC) and nitrogen (DON) released during litter decay. We conducted an experiment to investigate the impact of invertebrate shredder (Gammarus pulex) on metal/metalloid fixation/remobilization and on the quality of DOC/DON released under slightly acidic water conditions. During decomposition of leaf litter, invertebrate shredder facilitated significantly the emergence of smaller particle sizes of organic matter. The capacity of metal fixation was significantly higher in smaller particles (POM 2,000?C63???m) compared to original leaf litter and litter residues. Thus, G. pulex enhanced metal fixation by organic partition of sediments by increasing the amount of smaller particle of organic matter in aquatic ecosystems. In contrast, the capacity of metal/metalloid fixation in the smallest fraction of POM (<63???m) was lower compared with leaf residues in treatment without invertebrates. Remobilization of metals and metalloids was very low for all measured elements. A significant effect of invertebrates on quantitative formation of DOC/DON was confirmed. The quality of released DOC/DON, which may affect metal/metalloid remobilization, was also significantly affected by invertebrate shredders (e.g., more carboxylates). Hence, invertebrate shredder enhanced significantly the fixation of metals/metalloids into POM in slightly acidic environments.     

Heavy metals and arsenic fixation into freshwater organic matter under Gammarus pulex L. influence

Organic sediments are a main sink for metal pollutants in aquatic systems. However, factors that make sediments a sink of metals and metalloids are still not clear. Consequently, we investigate the role of invertebrate shredders (Gammarus pulex L.) on quality of metal and arsenic fixation into organic partitions of sediment in the course of litter decay with laboratory microcosm experiments. During the decomposition of leaf litter, G. pulex significantly facilitated the development of small particles of organic matter. The capacity of metal fixation was significantly higher in smaller particles than leaf litter and litter residuals. Thus, G. pulex enhanced metal fixation into the organic partition of sediments by virtue of increasing the amount smaller particles in the aquatic system. Furthermore, invertebrates have a significant effect on formation of dissolved organic matter and remobilization of cobalt, molybdenum and cesium, but no significant effect on remobilization of all other measured elements.     

Feedstock quality and growth of bioenergy crops fertilized with sewage sludge

Sewage sludge is rich in essential plant nutrients, but its use is restricted for crop production due to the pollutants it contains, such as metalloids and heavy metals. Sludge is also very sticky and compact. Therefore, the objectives of this work were to evaluate (1) the impact of various amounts of sludge on bioenergy crop productivity and quality and (2) the use of peat as an adjuvant to reduce the stickiness, density and nutrient richness of the sludge. Three different applications of sludge were examined, high, low (50% of high) and low mixed with an equal volume of peat. The sludge-peat mix increased significantly leaf area and biomass accumulation of maize and hemp. High sludge and sludge-peat mix applications increased significantly the leaf area and biomass accumulation as well as the net photosynthesis of oilseed rape. High sludge application resulted in the highest heavy metal and metalloid accumulation in maize and hemp. Sludge-peat mix resulted in the highest heavy metal and metalloid accumulation in oilseed rape. However, the sludge-peat mix application provided the best feedstock quality in all three crops, since chloride, silicon and sulfur concentrations and ash content in plant material were the lowest of the three sludge treatments.     

Plant accumulation of potentially toxic elements in sewage sludge as affected by soil organic matter level and mycorrhizal fungi.

Leek (Allium ameloprasum) was grown in pot trials in two clay loams of contrasting organic contents, with and without indigenous mycorrhizal propagules. Sewage sludges containing varying levels of Cd, Cu and Zn were added. Extractable soil metals, plant growth, major nutrient content and accumulation of metals, and soil microbial indices were investigated. The aim was to establish whether soil organic content and mycorrhizal status affected plant and microbial exposure to these metals. Extractable metals were higher and responses to inputs more pronounced in the arable, lower organic matter soil, although only Cd showed a soil difference in the CaCl2 fraction. There were no metal toxic effects on plants and some evidence to suggest that they promoted growth. Uptake of each metal was higher in the larger plants of the grassland, higher organic matter soil. Inoculation with arbuscular mycorrhizal fungi increased root Cd and Zn concentrations. With the exception of Cd (roots) and Zn (shoots), higher inputs of sludge metals did not increase plant metals. Zn and Cu, but not Cd, concentrations were higher in roots than in shoots.     

The effect of pH on plant litter decomposition and metal cycling in wetland mesocosms supplied with mine drainage

The long term effectiveness of compost-based wetland systems treating net-acidic mine waters is reliant upon a continuing supply of decomposed organic matter which provides the basic foodstock for sulphate reducing bacteria. The annual turnover of wetland vegetation within these systems has been suggested to be the primary source for this material once the original substrate has been consumed. This study aimed to determine whether plant litter (of Common Reed, Phragmites australis) decomposition rates and release of metals and nutrients were affected by pH using controlled experiments under laboratory conditions. Loss of plant biomass was found to be unaffected by pH (3.0-6.5) suggesting that plant litter could be an important source of organic molecules for bacterial populations even under acidic conditions. The decomposing plant litter also acted as a focus for the precipitation of Fe oxides and sorption of Zn thereby acting as a short-term sink for these contaminants. This has important implications for geochemical cycling within the wetland system and potential transport out of the system. The essential nutrients (K and Mg) released from plant litter were affected by pH which could be important in nutrient availability for re-use by vegetation and other organisms within the system.     

Agro-industrial wastes as effective amendments for ecotoxicity reduction and soil health improvement in aided phytostabilization

Aided phytostabilization is a technology that uses metal tolerant plants and organic and/or inorganic amendments to reduce soil metal bioavailability, while improving soil health. Our objective was to determine the effects of the application of amendments [sheep manure (SHEEP), poultry litter (POULTRY), cow slurry (COW), and paper mill sludge mixed with poultry litter (PAPER)], together with the growth of a metallicolous Festuca rubra L. population, on (i) chemical and microbial indicators of soil health and (ii) soil ecotoxicity, during the aided phytostabilization of a Zn/Pb contaminated mine soil. Amendment application led to an increase in soil pH, organic matter content, and inorganic salts, resulting in a decrease in Pb and Zn CaCl₂-extractable concentrations in soil, which, in turn, contributed to lower ecotoxicity and a stimulation of plant growth and soil microbial communities. The factor most affecting the metal extractability was probably soil pH. POULTRY was the best amendment in terms of increasing plant growth, chlorophylls content, and soil microbial biomass and activity, but resulted in higher levels of phytoavailable Pb and Zn. SHEEP and PAPER were more effective at reducing metal CaCl₂-extractability and, consequently, led to lower values of metal accumulation in plant tissues, thereby reducing the risk of metals entering into the food chain. When combined with the application of organic amendments, the metallicolous F. rubra population studied here appears an excellent candidate for aided phytostabilization. Our results indicate that the application of organic amendments is essential for the short-term recovery of highly contaminated metalliferous soils during aided phytostabilization.     

Dynamics of trace metals in organisms and ecosystems: prediction of metal bioconcentration in different organisms and estimation of exposure risks

Metal ions interact with biological materials and their decomposition products by ligation (coordination complex-formation with certain moieties containing O, N, S, etc.). The extent of this interaction depends on the identities of both ligand and metal ion and can be described by some equation derived from perturbation theory. Uptake of metal ions - including highly toxic ones - from soils is controlled by a competition between root exudate components and soil organic matter (SOM) for the ions. SOM consists of a variety of potential ligands which evolve during humification towards more efficient binding (retention) of metals such as Cu, Ni, Cr but also of toxicants like U, Cd. The actual way of interaction can be inferred from stoichiometry of the involved compounds and the C/N ratio in the soil, providing predictions as to which metals will be most efficiently shuttled into green plants or fungi, respectively. The latter, selective process is crucial for closing nutrient cycles and sensitively depends on C/N ratio and the extent of "forcing" by onfalling leaf or needle litter. Therefore, analytical data on the soil can be used to predict possible risks of exposition to toxic metals also for human consumption of plant parts.     

Glutathione and its dependent enzymes’ modulatory responses to toxic metals and metalloids in fish—a review

Toxic metals and metalloid are being rapidly added from multiple pathways to aquatic ecosystem and causing severe threats to inhabiting fauna including fish. Being common in all the type of aquatic ecosystems such as freshwater, marine and brackish water fish are the first to get prone to toxic metals and metalloids. In addition to a number of physiological/biochemical alterations, toxic metals and metalloids cause enhanced generation of varied reactive oxygen species (ROS) ultimately leading to a situation called oxidative stress. However, as an important component of antioxidant defence system in fish, the tripeptide glutathione (GSH) directly or indirectly regulates the scavenging of ROS and their reaction products. Additionally, several other GSH-associated enzymes such as GSH reductase (GR, EC 1.6.4.2), GSH peroxidase (EC 1.11.1.9), and GSH sulfotransferase (glutathione-S-transferase (GST), EC 2.5.1.18) cumulatively protect fish against ROS and their reaction products accrued anomalies under toxic metals and metalloids stress conditions. The current review highlights recent research findings on the modulation of GSH, its redox couple (reduced glutathione/oxidised glutathione), and other GSH-related enzymes (GR, glutathione peroxidase, GST) involved in the detoxification of harmful ROS and their reaction products in toxic metals and metalloids-exposed fish.     

Direct and indirect effects of metal contamination on soil biota in a Zn-Pb post-mining and smelting area (S Poland)

Effects of metal contamination on soil biota activity were investigated at 43 sites in 5 different habitats (defined by substratum and vegetation type) in a post-mining area. Sites were characterised in terms of soil pH and texture, nutrient status, total and exchangeable metal concentrations, as well as plant species richness and cover, abundances of enchytraeids, nematodes and tardigrades, and microbial respiration and biomass. The concentrations of total trace metals were highest in soils developed on mining waste (metal-rich dolomite), but these habitats were more attractive than sandy sites for plants and soil biota because of their higher content of organic matter, clay and nutrients. Soil mesofauna and microbes were strongly dependent on natural habitat properties. Pollution (exchangeable Zn and Cd) negatively affected only enchytraeid density; due to a positive relationship between enchytraeids and microbes it indirectly reduced microbial activity.     

Composting of spent pig litter at different seasonal temperatures in subtropical climate

To investigate the effects of seasonal temperatures on the composting of spent pig-manure sawdust litter (spent litter), two sets of experiments were carried out: one during winter, the other during summer. Physicochemical and microbial parameters including temperature, pH, inorganic N, humification indicators (HA and FA), heavy metals (Cu and Zn), total aerobic heterotrophs, ATP content and dehydrogenase activity were measured to understand changes in the spent litter during composting. Results demonstrated that the composting was faster during summer than winter. The spent litter during the summer trial reached maturity at day 56 whereas that of the winter trial was still immature at the end of composting (days 91). Microbial activities during the thermophilic stage of composting were much lower in the winter trial. Values began to increase during the latter part of composting, indicating that the spent litter in this winter trial was biologically unstable and must be further composted to reach full maturity. The changes in the microbial activities of the spent litter during summer or winter reflected the changes in their temperatures and chemical properties. The maturation of the spent litter during summer was accompanied by stabilization of the microbial and chemical properties and a drop in temperature to ambient level. Results of correlation analysis showed that temperature correlated not only with the microbial parameters but also with most of the chemical parameters. These parameters also correlated with each other. Among all the parameters measured, the trend of temperature changes is the simplest and most rapid parameter that can be used to evaluate the maturity of spent litter.     

The effects of a simulated acid precipitation on leaf litter quality and the growth of a detritivore in a buffered lotic system

The effects of a simulated acid rain on leaf litter quality and the growth of a detritivore in a buffered lotic system were investigated. Exposure of Populus balsamifera L. saplings to a simulated acid precipitation prior to leaf abscission resulted in significant decreases in foliar nitrogen content and increases in carbon: nitrogen ratios. During decomposition of the leaf litter in a buffered lotic system, microbial activity was significantly reduced. Growth of Tipula commiscibilis Diane (Diptera: Tipulidae) larvae decreased significantly when fed conditioned leaves exposed to a simulated acid precipitation prior to abscission. Reductions in detritivore growth were correlated with lower potential quality of the leaf litter resulting from increased carbon: nitrogen ratios and reduced levels of microbial activity. Thus, even in well buffered freshwater ecosystems, acid precipitation can have significant indirect effects on microbial activity and macroinvertebrate growth.     

Response of microbial activities to heavy metals in a neutral loamy soil treated with biosolid

Application of biosolid on land has been widespread in numerous countries for last several decades. This study performed incubation experiments by mixing a neutral loamy soil and biosolid enriched in Cu, Pb and Zn to explore how heavy metal affects soil mineralization and microbial biomass. The experimental results indicated that large nutrient, microorganism and C sources from biosolid were beneficial to microbial respiration. However, compared to the biosolid alone treatment, the supplemented Cu, Pb and Zn in biosolid reduced the mineralized C by roughly 36%. This phenomenon was probably caused by a portion of the Cu, Pb and Zn being complexed with organic matter to prevent decomposition of organic carbon by microorganisms. Equally, soil treated with biosolid increased the quantity of mineralized N by approximately five-fold and accelerated the rate of N mineralization by about one-fold compared to untreated soil. Notably, addition of heavy metals impaired the mineralization process, particularly when Pb reached about 64%. The reduced N mineralization occurred for similar reasons to the microbial respiration. The addition of biosolid in soil considerably increased the amount of mineralizable N; however, the increase was lower in biosolid-treated soil spiked by heavy metals. The addition of heavy metals in the soil-biosolid mixture clearly reduced the microbial biomasses C (MBC) and N (MBN), indicating that the microbial activities had been disrupted by the heavy metals. The microbial biomass C/N ratio had changed initially from 8 to 13 at the end of incubation period, owing to various groups of microbes expressing different mechanisms of metabolism, indicating that the microbial population had changed from bacteria to fungi, which had higher metal tolerance.     

Microbial cellulose decomposition in soils from a rifle range contaminated with heavy metals

The objective of this study was to assess the effects of heavy metals on microbial decomposition of cellulose in heavy metal-contaminated soils using a cotton strip assay. The assay is a measure of the potential of soil microorganisms to decompose the plant polymer, cellulose. Cellulolytic activity in soil was assessed by determining the reduction in tensile strength of the buried cotton strips over a 25- and 45-day period. Soils were obtained from a rifle range that contain high levels of lead, copper and zinc. The site has been used for approximately 50 years, resulting in metal levels of up to 30,000 mg/kg of lead, 4000 mg/kg of copper and 600 mg/kg of zinc in the most contaminated soils. All the metal-contaminated soils had lower degradation rates than the uncontaminated soils tested. Among the contaminated soils, however, the heavy metal concentration was not the major factor in determining the loss in tensile strength of the cotton strips, where cellulose decomposition was governed by other soil physicochemical properties. Soil with a higher cation exchange capacity, readily oxidisable material and volatile solids content had the greatest loss in tensile strength of cotton strips. Microbial adaptation to the presence of high concentrations of soil heavy metals and reduced bioavailability of metals is the likely explanation for this phenomenon.     

Influences of adding easily degradable organic waste on the minimization and humification of organic matter during straw composting

To find a better composting process with low greenhouse gas emission and high humus production, the effect of adding kitchen waste on reduction and humification of organic matter during straw composting was studied. Three processes were compared, consisting of different ratios of straw and kitchen waste (1:2, 1:1, and 2:1). At four time points over a 62-d incubation, the reduction and humification of compost was evaluated by measuring the total mass, carbon content, and humic material content of the compost. Treatment 1 (straw/kitchen waste ratio of 1:2) reduced the total mass of compost the most. Treatment 2 (straw/kitchen waste ratio of 1:1) reduced the total carbon content the most, reflecting the highest emission of greenhouse gas. Treatment 3 produced the most humic acid material and released the lowest amount of carbon. Hence, from the point of view of reducing greenhouse gas emissions and increasing stable organic matter such as humus and humic acid during composting, treatment #3 was optimal. The three treatments resulted in significant differences in microbial biomass and enzyme activity during composting. The highest amount of active microbial biomass was associated with the largest reduction in compost mass (treatment 1). Higher proportions of straw (treatments 2 and 3), which contains more lignin, were associated with greater β-glycosidase activity, which may generate more humus that can improve soil quality. Dehydrogenase activity seemed to be the most important microbial factor in organic carbon catabolism or humification.     

Effects of intense agricultural practices on heterotrophic processes in streams

In developed countries, changes in agriculture practices have greatly accelerated the degradation of the landscape and the functioning of adjacent aquatic ecosystems. Such alteration can in turn impair the services provided by aquatic ecosystems, namely the decomposition of organic matter, a key process in most small streams. To study this alteration, we recorded three measures of heterotrophic activity corresponding to microbial hydrolasic activity (FDA hydrolysis) and leaf litter breakdown rates with (k_c) and without invertebrates (k_f) along a gradient of contrasted agricultural pressures. Hydrolasic activity and k_f reflect local/microhabitat conditions (i.e. nutrient concentrations and organic matter content of the sediment) but not land use while k_c reflects land-use conditions. k_c, which is positively correlated with the biomass of Gammaridae, significantly decreased with increasing agricultural pressure, contrary to the taxonomic richness and biomass of Trichoptera and Plecoptera. Gammaridae may thus be considered a key species for organic matter recycling in agriculture-impacted streams.     

Eriophorum angustifolium and Lolium perenne metabolic adaptations to metals- and metalloids-induced anomalies in the vicinity of a chemical industrial complex

As plants constitute the foundation of the food chain, concerns have been raised about the possibility of toxic concentrations of metals and metalloids being transported from plants to the higher food chain strata. In this perspective, the use of important phytotoxicity endpoints may be of utmost significance in assessing the hazardous nature of metals and metalloids and also in developing ecological soil screening levels. The current study aimed to investigate the role of glutathione (GSH) and its associated enzymes in the metabolic adaptation of two grass species namely Eriophorum angustifolium Honck. and Lolium perenne L. to metals and metalloids stress in the vicinity of a chemical industrial complex (Estarreja, Portugal). Soil and plant samples were collected from contaminated (C) and non-contaminated (reference, R) sites, respectively, near and away from the Estarreja Chemical Complex, Portugal. Soils (from 0 to 10 and 10 to 20 cm depths) were analyzed for pH, organic carbon, and metals and metalloids concentrations. Plant samples were processed fresh for physiological and biochemical estimations, while oven-dried plant samples were used for metals and metalloids determinations following standard methodologies. Both soils and plants from the industrial area exhibited differential concentrations of major metals and metalloids including As, Cu, Hg, Pb, and Zn. In particular, L. perenne shoot displayed significantly higher and lower concentrations of Pb and As, respectively at contaminated site (vs. E. angustifolium). Irrespective of sites, L. perenne shoot exhibited significantly higher total GSH pool, oxidized glutathione (GSSG) and oxidized protein (vs. E. angustifolium). Additionally, severe damages to photosynthetic pigments, proteins, cellular membrane integrity (in terms of electrolyte leakage), and lipid peroxidation were also perceptible in L. perenne shoot. Contrarily, irrespective of the sites, activities of catalase and GSH-regenerating enzyme, GSH reductase, and GSH-metabolizing enzymes such as GSH peroxidase and GSH sulfotransferase were significantly higher in shoot of E. angustifolium. Despite the higher total GSH content, L. perenne is vulnerable to multi-metals-induced stress in comparison to E. angustifolium as depicted by increased GSH- and protein oxidation, low reactive oxygen radical-processing potential (exhibited in terms of low catalase activity) and poor GSH pool utilization efficiency (in terms of lower GSH-associated enzymes activities). The outcome of the present study may be significant for understanding vital GSH-mediated metals and metalloids tolerance mechanisms in plants as well as their unsuitability for animal consumption due to higher metals and metalloids burdens.     

Micro-spatial variation of soil metal pollution and plant recruitment near a copper smelter in Central Chile

Soil chemical changes produced by metal smelters have mainly been studied on a large scale. In terms of plant survival, determination of small scale variability may be more important because less toxic microhabitats may represent safe sites for successful recruitment and thus for plant survival. Three dominant microhabitats (open spaces and areas below the canopy of Sphaeralcea obtusiloba and Baccharis linearis shrubs) were defined in a heavily polluted area near a copper smelter and characterised in terms of microclimate, general soil chemistry, total and extractable metal concentrations in the soil profile (A0 horizon, 0-5 and 15-20 cm depth), and seedling densities. Results indicated a strong variability in microclimate and soil chemistry not only in the soil profile but also among microhabitats. Air/soil temperatures, radiation and wind speed were much lower under the canopy of shrubs, particularly during the plant growth season. Soil acidification was detected on top layers (0-5 cm depth) of all microhabitats while higher concentrations of N, Cu and Cd were detected on litter and top soil layers below shrubs when compared to open spaces; however, high organic matter content below shrubs decreased bioavailability of metals. Plant recruitment was concentrated under shrub canopies; this may be explained as a result of the nursery effect exerted by shrubs in terms of providing a more favourable microclimate, along with better soil conditions in terms of macronutrients and metal bioavailability.     

Changes in the chemical composition of water-extractable organic matter during composting: distribution between stable and labile organic matter pools

Aerobic decomposition and stabilization of organic matter during the composting of waste materials is primarily due to the biochemical transformation of water-soluble compounds in the liquid phase by the microbial biomass. For this reason water-soluble organic matter represents the most active fraction of compost, both biologically and chemically, and thus should directly reflect the biochemical alteration of organic matter. This work aims to elucidate the microbial-mediated processes responsible for the distribution of soluble organic matter between stable and labile pools with composting time. Accordingly, chemical analysis as well as UV absorption, and ¹H and ¹³C-NMR spectroscopy of samples collected during the industrial composting of urban waste revealed microbial induced transformation of water-extractable organic matter over time. The chemical composition changed from labile, hydrophilic, plant-derived organic compounds in the beginning to predominately stable, hydrophobic moieties comprising lignin-derived phenols and microbially-derived carbohydrates at later stages of composting.     

The influence of pH and organic matter content in paddy soil on heavy metal availability and their uptake by rice plants

The experiments were done to investigate the effect of soil pH and organic matter content on EDTA-extractable heavy metal contents in soils and heavy metal concentrations in rice straw and grains. EDTA-extractable Cr contents in soils and concentrations in rice tissues were negatively correlated with soil pH, but positively correlated with organic matter content. The combination of soil pH and organic matter content would produce the more precise regression models for estimation of EDTA-Cu, Pb and Zn contents in soils, demonstrating the distinct effect of the two factors on the availability of these heavy metals in soils. Soil pH greatly affected heavy metal concentrations in rice plants. Furthermore, inclusion of other soil properties in the stepwise regression analysis improved the regression models for predicting straw Fe and grain Zn concentrations, indicating that other soil properties should be taken into consideration for precise predicting of heavy metal concentrations in rice plants.     

Cu sorption on Phragmites australis leaf and stem litter: a kinetic study

Decaying organic matter plays an important role in the cycling of metals in wetland ecosystems. Sorption kinetics of Cu(II) on Phragmites australis leaf and stem litter were studied. Fresh leaf and stem litter was sampled from a surface flow wetland at the end of the growing season. The effect of decomposition stage was studied with litter that had been decomposing for a period of 5 months. The Lagergren pseudo-first-order model, the pseudo-second-order model, the Elovich equation and two diffusion models based on spherical intra-particle diffusion were fitted to the experimental data. The sorption capacity was significantly affected by the decomposition of the litter. The sorption process was best described by the pseudo-second-order kinetics (R(2) approximately 0.99) but the rate constant was strongly dependent on the initial Cu concentration. The intra-particle diffusion model fitted the data only slightly less (R(2)>0.95) than the pseudo-second-order model. A theoretical comparison revealed that the good fit with the pseudo-second-order kinetics could be indicative of intra-particle diffusion. Sorption kinetics observed for the leaf and stem litter at different metal concentrations showed a fast initial sorption followed by a slow sorption phase.