Effect of metals on a siderophore producing bacterial isolate and its implications on microbial assisted bioremediation of metal contaminated soils

A bacterial isolate producing siderophore under iron limiting conditions, was isolated from mangroves of Goa. Based on morphological, biochemical, chemotaxonomical and 16S rDNA studies, the isolate was identified as Bacillus amyloliquefaciens NAR38.1. Preliminary characterization of the siderophore indicated it to be catecholate type with dihydroxy benzoate as the core component. Optimum siderophore production was observed at pH 7 in mineral salts medium (MSM) without any added iron with glucose as the carbon source. Addition of NaCl in the growth medium showed considerable decrease in siderophore production above 2% NaCl. Fe⁺² and Fe⁺³ below 2 μM and 40 μM concentrations respectively, induced siderophore production, above which the production was repressed. Binding studies of the siderophore with Fe⁺² and Fe⁺³ indicated its high affinity towards Fe⁺³. The siderophore concentration in the extracellular medium was enhanced when MSM was amended with essential metals Zn, Co, Mo and Mn, however, decreased with Cu, while the concentration was reduced with abiotic metals As, Pb, Al and Cd. Significant increase in extracellular siderophore production was observed with Pb and Al at concentrations of 50 μM and above. The effect of metals on siderophore production was completely mitigated in presence of Fe. The results implicate effect of metals on the efficiency of siderophore production by bacteria for potential application in bioremediation of metal contaminated iron deficient soils especially in the microbial assisted phytoremediation processes.     

Salicylic acid involved in the regulation of nutrient elements uptake and oxidative stress in Vallisneria natans (Lour.) Hara under Pb stress

In this study, the alterations in nutrient elements content, reactive oxygen species level and antioxidant response were studied in leaves of Vallisneria natans (Lour.) Hara exposed to salicylic acid (SA, 10 or 100 μM), or Pb (50 μM) or their combinations for 4 d. No significant alterations in Mn and Ca content were observed but content of Cu, Zn, Fe and P decreased in plants exposed to SA alone. SA application inhibited the uptake of Pb and partially reversed Pb-induced the alterations in Mn, Ca and Fe content in leaves of V. natans exposed to 50 μM Pb. The decreased chlorophyll (a + b) and increased malondialdehyde and O²⁻ and H₂O₂ content were detected in plants exposed to 100 μM SA, 50 μM Pb, 10 μM SA + 50 μM Pb or 100 μM SA + 50 μM Pb. Application SA partially inhibited Pb-induced the increase of malondialdehyde, O²⁻ and H₂O₂ content. 100 μM SA decreased the activity of NADH oxidase and the content of non-protein thiols, carotenoids and ascorbic acid and increased the content of dehydroascorbate in plants treated with or without Pb. SA alone decreased the ascorbate peroxidase activity and increased the catalase and peroxidase activity, while SA application increased catalase activity but had no significant effect on ascorbate peroxidase and peroxidase activity in V. natans exposed to Pb. The results indicate that SA involves in the regulation of Pb uptake, nutrient balance and oxidative stress.     

The effect of EDDS and citrate on the uptake of lead in hydroponically grown Matthiola flavida

Root and shoot lead concentrations and the impact of chelating agents on these were investigated in two populations of the novel metallophyte Matthiola flavida. Plants were exposed in hydroponics to Pb(NO₃)₂, supplied alone, or in combination with citric acid, or EDDS. When supplied at concentrations expected to bind about 95% of the Pb in a solution containing 1-μM Pb (1000 μM citrate or 3.1 μM EDDS, respectively), the root and shoot Pb concentrations were dramatically lowered, in comparison with a 1-μM free ionic Pb control exposure. A 1-mM EDDS + 1-μM Pb treatment decreased the plants’ Pb concentrations further, even to undetectable levels in one population. At 100 μM Pb in a 1-mM EDDS-amended solution the Pb concentration increased strongly in shoots, but barely in roots, in comparison with the 1-μM Pb + 1-mM EDDS treatment, without causing toxicity symptoms. Further increments of the Pb concentration in the 1-mM EDDS-amended solution, i.e. to 800 and 990 μM, caused Pb hyperaccumulation, both in roots and in shoots, associated with a complete arrest of root growth and foliar necrosis. M. flavida seemed to be devoid of constitutive mechanisms for uptake of Pb-citrate or Pb-EDDS complexes. Hyperaccumulation of Pb-EDDS occurred only at high exposure levels. Pb-EDDS was toxic, but is much less so than free Pb. Free EDDS did not seem to be toxic at the concentrations tested.     

Metal sorption by peat and algae treated peat: kinetics and factors affecting the process

The article presents a new approach that can be used for the purification of water contaminated by heavy metals. The treatment of peat with microalgae showed to be an effective way of increasing metal uptake by peat. Metal sorption was studied for a multimetal solution containing Cu, Cd, Ni, Zn, Cd, and Pb. Cu and Pb were found to be the metals having the highest affinity to peat. Water hardness has a strong effect on the uptake of borderline metals (Cd, Ni, Zn, Cd) from a solution. The use of algae for peat treatment resulted in less time to reach an equilibrium (24 h vs. 72 h for pure peat), and the effect of water hardness (Ca²⁺) on metal uptake was considerably reduced. Both peat and algal-treated peat were able to take up metals from rather acidic solutions (pH 3.0). pH had less influence on the metal uptake compared with water hardness. The affinity of heavy metals to peat was the following: Pb > Cu > Ni > Cd > Zn > Co. It slightly changed to Pb > Cu > Ni > Cd ≈ Co ≈ Zn when the combined sorbent, peat treated with microalga, was applied.     

Freshwater Ulva (Chlorophyta) as a bioaccumulator of selected heavy metals (Cd, Ni and Pb) and alkaline earth metals (Ca and Mg)

We analyzed the ability of freshwater taxa of the genus Ulva (Ulvaceae, Chlorophyta) to serve as bioindicators of metal in lakes and rivers. Changes in heavy metal (Ni, Cd and Pb) and alkaline earth metal (Ca and Mg) concentrations in freshwater Ulva thalli were investigated during the period from June to August 2010. The study was conducted in two ecosystems in Western Poland, the Malta lake (10 sites) and the Nielba river (six sites). Three components were collected for each sample, including water, sediment and Ulva thalli. The average concentrations of metals in the water sample and in the macroalgae decreased in the following order: Ca > Mg > Ni > Pb > Cd. The sediment revealed a slightly altered order: Ca > Mg > Pb > Ni > Cd. Ca and Mg were found at the highest concentrations in thalli due to the presence of carbonate on its surface. Among the examined heavy metals in thalli, Ni was in the highest concentration, and Cd found in the lowest concentration. There were statistically significant correlations between the levels of metals in macroalgae, water and sediment. Freshwater populations of Ulva exhibited a greater efficiency to bioaccumulate nickel as compared to species derived from marine ecosystems.     

Histopathological effects of copper and lithium in the ramshorn snail, Marisa cornuarietis (Gastropoda, Prosobranchia)

The aim of this study was to determine and quantify effects of copper and lithium in tissues of early juveniles of the ramshorn snail, Marisa cornuarietis. For this purpose, hatchlings of M. cornuarietis were exposed for 7 days to a range of five different sublethal concentrations of copper (5, 10, 25, 50, and 75 μg Cu²⁺ L⁻¹) and lithium (50, 100, 200, 1000, and 5000 μg Li⁺ L⁻¹). Both metals changed the tissue structure of epidermis, hepatopancreas, and gills, varying between slight and strong reactions, depending on the copper and lithium concentration. The histopathological changes included alterations in epithelial and mucous cells of the epidermis, swelling of hepatopancreatic digestive cells, alterations in the number of basophilic cells, abnormal apices of digestive cells, irregularly shaped cilia and changes in the amount of mucus in the gills. The most sensible organ in M. cornuarietis indicating Cu or Li pollution is the hepatopancreas (LOECs were 10 μg Cu²⁺ L⁻¹, or 200 μg Li⁺ L⁻¹). In epidermis, mantle and gills relevant effects occurred with higher LOECs (50 μg Cu²⁺ L⁻¹, or 1000 μg Li⁺ L⁻¹). Base on LOECs, our results indicated that histopathological endpoints are high sensitivity to copper and lithium compared to endpoints for embryonic developmental toxicity.     

Aerobic degradation of tetrabromobisphenol-A by microbes in river sediment

This study investigated the aerobic degradation of tetrabromobisphenol-A (TBBPA) and changes in the microbial community in river sediment from southern Taiwan. Aerobic degradation rate constants (k₁) and half-lives (t_1/2) for TBBPA (50 μg g⁻¹) ranged from 0.053 to 0.077 d⁻¹ and 9.0 to 13.1 d, respectively. The degradation of TBBPA (50 μg g⁻¹) was enhanced by adding yeast extract (5 mg L⁻¹), sodium chloride (10 ppt), cellulose (0.96 mg L⁻¹), humic acid (0.5 g L⁻¹), brij 30 (55 μM), brij 35 (91 μM), rhamnolipid (130 mg L⁻¹), or surfactin (43 mg L⁻¹), with rhamnolipid yielding a higher TBBPA degradation than the other additives. For different toxic chemicals in the sediment, the results showed the high-to-low order of degradation rates were bisphenol-A (BPA) (50 μg g⁻¹) > nonylphenol (NP) (50 μg g⁻¹) > 4,4′-dibrominated diphenyl ether (BDE-15) (50 μg g⁻¹) > TBBPA (50 μg g⁻¹) > 2,2′,3,3′,4,4′,5,5′,6,6′-decabromodiphenyl ether (BDE-209) (50 μg g⁻¹). The addition of various treatments changed the microbial community in river sediments. The results also showed that Bacillus pumilus and Rhodococcus ruber were the dominant bacteria in the process of TBBPA degradation in the river sediments.     

Partitioning of Cd and Pb in the blood of European blackbirds (Turdus merula) from a smelter contaminated site and use for biomonitoring

Blood composition is commonly measured to assess exposure to and effects of metals on birds. In most of passerine species, only small volumes of blood may be sampled safely (<500 μL), which limit the measure of several markers of health status and chemical residues. Here, we documented the partitioning of Cd and Pb in the blood of European Blackbirds Turdus merula in order to propose usable relationships between whole blood concentrations (for which toxicological benchmarks exist) and those measured in the erythrocytes. Sixty-two blackbirds were trapped along a pollution gradient (smelter of Metaleurop Nord, Northern France). Blood was sampled and Cd and Pb concentrations were measured both in whole blood and in the erythrocytes only. Birds coming from the most contaminated sites exhibited high residues for both Cd and Pb. We assessed that 73% and 99% of Cd and Pb, respectively, were associated to erythrocytes. Strong linear relationships, that were not influenced by neither the age nor the sex, were established between whole blood residues and those of erythrocytes for Cd and Pb (adj-R² = 0.78 and 0.93, respectively). Present findings are promising to optimize the use of small blood samples in order to investigate several responses relative to wildlife health status.     

The association between total urinary arsenic concentration and renal dysfunction in a community-based population from central Taiwan

Arsenic (As) is an important environmental toxicant that can cause cancer and cardiovascular disease, but the relationship between As exposure and renal dysfunction is not clear. The aim of this study is to examine the association between As exposure and renal dysfunction in a community-based population in central Taiwan. One thousand and forty-three subjects were recruited between 2002 and 2005. The risk for type 2 diabetes was increased by 2-fold (p < 0.05) in subjects with total urinary As (U-As) > 75 μg g⁻¹ creatinine as compared with subjects whose U-As was ?35 μg g⁻¹ creatinine after the adjustment for potential confounders. The adjusted odds ratio for an abnormal β2 microglobulin (B2MG > 0.154 mg L⁻¹) was significantly higher in subjects with U-As > 35 μg g⁻¹ creatinine as compared with the reference group adjusted for age, sex, living area, cigarette smoking, diabetes, and hypertension. The risk for abnormal B2MG and estimated glomerular filtration rate (eGFR < 90 mL min⁻¹ (1.73 m²)⁻¹) was both increased around 2-fold (p < 0.05) in subjects with U-As > 75 μg g⁻¹ creatinine as compared with those with U-As ? 35 μg g⁻¹ creatinine adjusted for all the risk factors plus lead (Pb), cadmium and nickel. The prevalence of abnormal B2MG was 4.82 times higher in subjects with both over the median levels of U-As (85.1 μg L⁻¹) and urinary Pb (18.9 μg L⁻¹) as compared to both lower than the median (p < 0.001). These results indicate that U-As might relate to renal dysfunction even other important risk factors were taken into account. Follow-up studies for causal inference are warranted.     

Industrial wastewater pre-treatment for heavy metal reduction by employing a sorbent-assisted ultrafiltration system

This work examined the adoption of a sorbent-assisted ultrafiltration (UF) system for the reduction of Pb(II), Cu(II), Zn(II) and Ni(II) from industrial wastewater. In such a system metals were removed via several processes which included precipitation through the formation of hydroxides, formation of precipitates/complexes among the metal ions and the wastewater compounds, adsorption of metals onto minerals (bentonite, zeolite, vermiculite) and retention of insoluble metal species by the UF membranes. At pH = 6 the metal removal sequence obtained by the UF system was Pb(II) > Cu(II) > Zn(II) > Ni(II) in mg g⁻¹ with significant amount of lead and copper being removed due to chemical precipitation and formation of precipitates/complexes with wastewater compounds. At this pH, zinc and nickel adsorption onto minerals was significant, particularly when bentonite and vermiculite were employed as adsorbents. Metal adsorption onto zeolite and bentonite followed the sequence Zn(II) > Ni(II) > Cu(II) > Pb(II), while for vermiculite the sequence was Ni(II) > Zn(II) > Cu(II) > Pb(II) in mg g⁻¹. The low amount of Pb(II) and Cu(II) adsorbed by minerals was attributed to the low available lead and copper concentration. At pH = 9 the adoption of UF could effectively reduce heavy metals to very low levels. The same was observed at pH = 8, provided that minerals were added. The prevailing metal removal process was the formation of precipitates/complexes with wastewater compounds.     

Concentrations and bioaccessibilities of metals in exterior urban paints

Paint fragments have been collected from a variety of structures (e.g. walls, lamp posts, doors, railings) from the urban environment of Plymouth, UK, and concentrations of metals determined following acid digestion. Concentrations of most metals were highly variable and spanned several orders of magnitude among the samples (e.g. Pb = 4.5 to 36 900 μg g⁻¹; Cr = 1.9 to 775 μg g⁻¹; Zn = 39 to 23 500 μg g⁻¹). The bioaccessibilities of the metals were evaluated using a physiologically based extraction test that simulates the chemical conditions of the human stomach and intestine. The bioaccessibility of a given metal was highly variable among the samples and was greater in the stomach than the intestine in some cases (e.g. Cd, Pb) and greater in the intestine in others (e.g. Co, Cr). Based on total and bioaccessible concentrations in urban paints, Pb remains the metal of greatest concern from a human health perspective.     

Accumulation and quantitative estimates of airborne lead for a wild plant (Aster subulatus)

Foliar uptake of airborne lead is one of the pathways for Pb accumulation in plant organs. However, the approximate contributions of airborne Pb to plant organs are still unclear. In the present study, aerosols (nine-stage size-segregated aerosols and total suspended particulates), a wild plant species (Aster subulatus) and the corresponding soils were collected and Pb contents and isotopic ratios in these samples were analyzed. Average concentration of Pb was 96.5 ± 63.5 ng m⁻³ in total suspended particulates (TSP) and 20.4 ± 5.5 ng m⁻³ in the fine fractions of size-segregated aerosols (SSA) (<2.1 μm), higher than that in the coarser fractions (>2.1 μm) (6.38 ± 3.71 ng m⁻³). Enrichment factors show that aerosols and soils suffered from anthropogenic inputs and the fine fractions of the size-segregated aerosols enriched more Pb than the coarse fractions. The order of Pb contents in A. subulatus was roots > leaves > stems. The linear relationship of Pb isotope ratios (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb) among soil, plant and aerosol samples were found. Based on the simple binary Pb isotopic model using the mean ²⁰⁶Pb/²⁰⁷Pb ratios in TSP and in SSA, the approximate contributions of airborne Pb into plant leaves were 72.2% and 65.1%, respectively, suggesting that airborne Pb is the most important source for the Pb accumulation in leaves. So the combination of Pb isotope tracing and the simple binary Pb isotope model can assess the contribution of airborne Pb into plant leaves and may be of interest for risk assessment of the exposure to airborne Pb contamination.     

Trace metals in Ganges soft-shell turtle (Aspideretes gangeticus) from two barrage: Baloki and Rasul, Pakistan

The concentration of nine metals was measured in liver, kidney, heart, muscle, plastron, and carapace of Aspideretes gangeticus from Rasul and Baloki barrages, Pakistan. The results indicated that metal concentration were significant different among tissues of Ganges soft-shell turtles. However, higher concentrations of Co (5.12 μg/g) and Ni (1.67 μg/g) in liver, Cd (0.41 μg/g) in heart, Fe (267.45 μg/g), Cd (2.12 μg/g) and Mn (2.47 μg/g) in kidney, Cd (0.23 μg/g), Cu (2.57 μg/g), Fe (370.25 μg/g), Mn (5.56 μg/g), and Pb (8.23 μg/g) in muscle of A. gangeticus were recorded at Baloki barrage than Rasul barrage. Whereas mean concentrations of Pb (3.33 μg/g) in liver, Co (1.63 μg/g), Cu (11.32 μg/g), Pb (4.8 μg/g) and Zn (144.69 μg/g) in heart, Co (4.12 μg/g) in muscle, Ni (1.31 μg/g), Pb (2.18 μg/g), and Zn (9.78 μg/g) in carapace were recorded higher at Rasul barrage than Baloki barrage. The metals followed the trend Fe > Zn > Ni > Cu > Mn > Pb > Cr > Co > Cd. Metals of toxicological concern such as Cr, Pb, and Cd were at that level which can cause harmful effects to turtles. The results provide baseline data of heavy metals on freshwater turtle species of Pakistan.     

Relationships between hepatic trace element concentrations, reproductive status, and body condition of female greater scaup

We collected female greater scaup (Aythya marila) on the Yukon-Kuskokwim Delta, Alaska during two breeding seasons to determine if concentrations of 18 trace elements in livers and eggs were elevated and if hepatic concentrations correlated with body condition or affected reproductive status. Fifty-six percent, 5%, and 42% of females, respectively, had elevated hepatic cadmium (Cd: >3 μg g⁻¹ dry weight [dw]), mercury (Hg: >3 μg g⁻¹ dw), and selenium (Se: >10 μg g⁻¹ dw). Somatic protein and lipid reserves were not correlated with hepatic Cd or Hg, but there was a weak negative correlation between protein and Se. Hepatic Cd, Hg, and Se were similar in females that had and had not initiated egg production. In a sample of six eggs, 33% and 100%, respectively, contained Se and Hg, but concentrations were below embryotoxicity thresholds. We conclude that trace element concentrations documented likely were not adversely impacting this study population.     

Effect of microbial siderophore DFO-B on Cd accumulation by Thlaspi caerulescens hyperaccumulator in the presence of zeolite

Hyperaccumulators are grown in contaminated soil and water in order that contaminants are taken up and accumulated. Transport of metals from soil to plant is initially dependent on the solubility and mobility of metals in soil solution which is controlled by soil and metal properties and plant physiology. Complexation with organic and inorganic ligands may increase mobility and availability of metals for plants. In this work the influence of desferrioxamine-B (DFO-B), which naturally is produced in the rhizosphere, and zeolite on Cd accumulation in root and shoot of Thlaspi caerulescens (Cd hyperaccumulator) was investigated. Plants were grown in pots with clean quartz sand, amended with 1% zeolite; treatment solutions included 0, 10, and 100 μM Cd and 70 μM DFO-B. Addition of zeolite to the quartz sand significantly reduced Cd concentration in plant tissues and translocation from root to shoot. On contrary, DFO-B considerably enhanced Cd sorption by roots and translocation to aerial part of plants. Treating the plants with zeolite and DFO-B together at 10 μM Cd resulted in reduction of the bioaccumulation factor but enhancement of Cd translocation from root to shoot at the rate of 13%. In contrast, at 100 μM Cd in the solution both bioaccumulation and translocation factors decreased. Total metal accumulation as a key factor for evaluating the efficiency of phytoremediation was highly influenced by treatments. Presence of zeolite in pots significantly decreased total Cd accumulation by plants, whereas, DFO-B clearly enhanced it.     

Dissolution of mimetite Pb5(AsO4)3Cl in low-molecular-weight organic acids and EDTA

Due to its relatively low solubility, mimetite Pb₅(AsO₄)₃Cl may control Pb and As(V) solution levels at a low value in contaminated soils. The time-dependent dissolution of mimetite by low-molecular-weight organic acids (LMWOAs) such as acetic, lactic, citric, and ethylene diamine tetra-acetic acid (EDTA) was determined. At pH 3.5, the presence of citric acid or EDTA significantly increases the solubility of mimetite while acetic or lactic acids show little effect. The effect of all organic anions on the dissolution of mimetite increased with the increase in solution pH. The rate of mimetite dissolution depended on the kind and concentration of organic solvents in the sequence r_EDTA > r_lactate > r_acetate > r_citrate. Soluble Pb and As(V) released in LMWOAs and EDTA were higher than the WHO guideline value for these elements in drinking water (10 μg As(V) L⁻¹, 10 μg Pb L⁻¹). This suggests that soil organic acids in rhizosphere can potentially liberate Pb and As(V) from mimetite in contaminated soils.     

Salinity increases mobility of heavy metals in soils

The effect of salinity induced by CaCl₂, MgCl₂, NaCl and Na₂SO₄ on the mobility of Cu, Cd, Pb and Zn was studied. An increase of ionic strength by any salts promoted a higher release of Cd than the others metals. When CaCl₂ and NaCl were applied, Cd and Pb showed the highest degree of mobilization. When MgCl₂ was applied, Cd and Cu were mobilized the most. Finally, an increase of Na₂SO₄ also promoted the strongest mobilization of Cd and Cu.As the total heavy metal content was higher, the percentage of Pb and Cu released upon salinization decreased, indicating that these metals are strongly bound to soil constituents. An increase of carbonates in the soil promoted a higher release of Pb for all used salts and for Zn when MgCl₂ and NaCl were used. This indicates that Pb and Zn are adsorbed on the surface of carbonate crystals. An increase of fine particles promoted a decrease of percentage of released Cd for all salts, indicating that Cd is strongly retained in the fine fractions.The main mechanism regulating Pb and Cd mobility was competition with Ca²⁺ for sorption sites followed for metal chloro-complexation, association between the Cd/Pb-sulfates and competition with Mg²⁺. The main mechanism regulating Cu mobility was the formation of Cu-sulfate, followed by competition with cations (Mg > Ca) and chloride. For Zn, competition with Ca²⁺ for sorption sites was the most important process for its mobility; followed by Zn-sulfate association and, finally, chloride and competition with Mg with the same effect.     

The exposition of a calcareous Mediterranean soil to toxic concentrations of Cr, Cd and Pb produces changes in the microbiota mainly related to differential metal bioavailability

The involvement of the bacterial community of an agricultural Mediterranean calcareous soil in relation to several heavy metals has been studied in microcosms under controlled laboratory conditions. Soil samples were artificially polluted with Cr(VI), Cd(II) and Pb(II) at concentrations ranging from 0.1 to 5000 mg kg⁻¹ and incubated along 28 d. The lowest concentrations with significant effects in soil respirometry were 10 mg kg⁻¹ Cr and 1000 mg kg⁻¹ Cd and Pb. However, only treatments showing more than 40% inhibition of respirometric activity led to significant changes in bacterial composition, as indicated by PCR-DGGE analyses. Presumable Cr- and Cd-resistant bacteria were detected in polluted microcosms, but development of the microbiota was severely impaired at the highest amendments of both metals. Results also showed that bioavailability is an important factor determining the impact of the heavy metals assayed, and even an inverted potential toxicity ranking could be achieved if their soluble fraction is considered instead of the total concentration. Moreover, multiresistant bacteria were isolated from Cr-polluted soil microcosms, some of them showing the capacity to reduce Cr(VI) concentrations between 26% and 84% of the initial value. Potentially useful strains for bioremediation were related to Arthrobacter crystallopoietes, Stenotrophomonas maltophilia and several species of Bacillus.     

Oxidation of bisphenol F (BPF) by manganese dioxide

Bisphenol F (BPF), an environmental estrogen, is used as a monomer in plastic industry and its environmental fate and decontamination are emerging concern. This study focused on the kinetics, influencing factors and pathways of its oxidation by MnO₂. At pH 5.5, about 90% of BPF was oxidized in 20 min in a solution containing 100 μM MnO₂ and 4.4 μM BPF. The reaction was pH-dependent, following an order of pH 4.5 > pH 5.5 > pH 8.6 > pH 7.5 > pH 6.5 > pH 9.6. Humic acids inhibited the reaction at low (≤pH 5.5) and high pH (≥pH 8.6) at high concentrations. In addition, metal ions and anions also suppressed the reaction, following the order Mn²⁺ > Ca²⁺ > Mg²⁺ > Na⁺ and HPO₄²⁻ > Cl⁻ > NO₃⁻ ≈ SO₄²⁻, respectively. A total of 5 products were identified, from which a tentative pathway was proposed.     

Mercury, cadmium and lead concentrations in different ecophysiological groups of earthworms in forest soils

Bioaccumulation of Hg, Cd and Pb by eight ecophysiologically distinct earthworm species was studied in 27 polluted and uncontaminated forest soils. Lowest tissue concentrations of Hg and Cd occurred in epigeic Lumbricus rubellus and highest in endogeic Octolasion cyaneum. Soils dominated by Dendrodrilus rubidus possess a high potential of risk of Pb biomagnification for secondary predators. Bioconcentration factors (soil-earthworm) followed the sequence ranked Cd > Hg > Pb. Ordination plots of redundancy analysis were used to compare HM concentrations in earthworm tissues with soil, leaf litter and root concentrations and with soil pH and CEC. Different ecological categories of earthworms are exposed to Hg, Cd and Pb in the topsoil by atmospheric deposition and accumulate them in their bodies. Species differences in HM concentrations largely reflect differences in food selectivity and niche separation.