The Zn abundance and isotopic composition of diatom frustules,a proxy for Zn availability in ocean surface seawater

We have developed cleaning methods for extracting diatomopal from bulk marine sediment samples, for measurement of both zinc (Zn) abundance and isotope composition. This cleaning technique was then applied to a set of Holocene core-top samples from the Southern Ocean. The measured δ⁶⁶Zn (reported relative to the JMC_Lyon standard) and Zn/Si ratios from the Southern Ocean diatom_opal samples range from 0.7 to 1.5‰, and from 14 to 0.9 μmol/mol, respectively. The Zn abundance and isotope composition data show a clear correlation with opal burial rates and other oceanographic parameters. In common with previous work, we interpret the systematic changes in the Zn/Si ratio to be linked to the variability in the concentrations of bioavailable Zn in the ambient surface seawater where the diatom opal is formed. This variability is likely to be primarily controlled by the degree to which Zn is taken up into phytoplankton biomass. The observed systematic pattern in the δ⁶⁶Zn compositions of the diatom_opal core-top samples is, similarly, likely to reflect changes in the δ⁶⁶Zn composition of the ambient Zn in the surface waters above the core-top sites, which is progressively driven towards isotopically heavier values by preferential incorporation of the lighter isotopes into phytoplankton organic material. Thus, the systematic relationship between Zn isotopes and abundance observed in the core-top diatom_opal samples suggests a potential tool for investigating the biogeochemical cycling of Zn in the past surface ocean for down-core diatom_opal material. In this respect, it may be possible to test hypotheses that attribute variations in atmospheric CO₂ on glacial–interglacial timescales to the degree to which trace metals limited primary productivity in HNLC zones.     

Concentrations of Cd, Pb, Zn and Cu in pristine wetlands of the Russian Arctic

Background concentrations of Cd, Pb, Zn and Cu were studied for wetlands from pristine regions of the Russian Arctic: Severnaya Zemlya Archipelago, Vrangel Island, Arctic deserts and tundra of the North Taimyr Peninsula, Byrranga Mountainous Area, tundra zone of Mid-Siberia, North-East Siberia, Far North-East, and Amguemo-Anadyr Mountainous Area. These wetland regions were known to be relatively remote and isolated, with little human population and no local industry. Samples were collected during the period 1976–1993 and included: (a) snow and thaw water, (b) particulate matter, (c) bottom sediments, (d) hydric organo-mineral deposits and hydric soils, (e) polygonal bog peat and sedge-moss peat. Observed ranges for the background concentrations of Cd, Pb, Zn, and Cu in water were 0.001–0.15, 0.02–0.36, 0.05–2.9 and 0.23–6.2 μg l⁻¹ respectively. For (b)–(e) the corresponding values were [0.04–0.46; 1.3–41; 8.6–190; 0.7–63]; [0.05 0.99; 1.5–49; 2.5–153; 2.4–55]; [0.05–0.96; 1.7–44; 2.2–154; 2.0–82] and [0.03–0.83; 1.3–31; 2.1–124; 1.7–68] mg kg⁻¹, dry wt, respectively. Although full assessment of the pristine nature of the wetlands was not possible due to the limited data available, the observed metal concentrations reflect natural geochemical background levels and influence from localized minor ore-deposits present for some regions. In general, there was no evidence of impact from remote industrial regions of the Russian Arctic.     

Concentrations of Cd, Pb, Zn and Cu in contaminated wetlands of the Russian Arctic

The spatial distribution of the concentrations of heavy metals Cd, Pb, Zn and Cu were studied for contaminated wetlands located by industrial centres and villages influenced by anthropogenic contamination in the Russian Arctic. For comparison, non-contaminated wetlands were also studied in neighbouring areas. Samples were collected during the period 1977–1994 and included: (a) water, (b) particulate matter, (c) bottom sediments, (d) hydric soils and (e) hummock bog peat and polygonal bog peat. For impacted wetlands, the observed ranges for the concentrations of Cd, Pb, Zn, and Cu in water were 0.12–0.8, 0.9–2.5, 2.4–15 and 16–34 μg l⁻¹, respectively. For (b)- (e) the corresponding values were [1.2–5.4; 24–37; 120–320; 80–116]; [6.4–17; 34–59; 240–570; 115–280]; [10–32; 57–78; 315–480; 87–350] and [5.1–53; 51–150; 125–520; 80–440] mg/kg, dry wt, respectively. The metal concentrations were up to 1000 times higher than background levels determined for non-contaminated wetlands in the Russian Arctic. The contaminants appear to be a direct result of localized anthropogenic activity, arising primarily from geoprospecting, the oil and coal industry, and domestic waste.     

Phytoremediation of Sb,As, Cu,and Zn from Contaminated Water by the Aquatic Macrophyte Eleocharis acicularis

Sb, As, Cu, and Zn toxicity and contamination have become a growing concern in recent years. Phytoremediation, a plant based and cost effective technology, may be an effective approach in the cleanup of water contaminated by these metals. In this study, the aquatic macrophyte Eleocharis acicularis was used in laboratory and field experiments to assess its capability to accumulate Sb, As, Cu, and Zn, and thereby investigate its potential application in phytoremediation. The results showed that E. acicularis adapted well to water contaminated by these metals. The removal rates of Sb, As, Cu, and Zn in the laboratory experiment were 3.04, 2.75, 0.417, and 1.49 μg/L/day, respectively. The highest concentrations of these metals accumulated in E. acicularis after 10 days of the laboratory experiment were 6.29, 6.44, 20.5, and 73.5 mg/kg dry weight, respectively. Only 8% of As, 12% of Sb, 87% of Cu and 93% of Zn removed from the water were used by E. acicularis. The highest concentrations of Sb, As, Cu, and Zn accumulated in E. acicularis after 10 wk of the field experiment were 76.0, 22.4, 33.9, and 266 mg/kg dry weight, respectively. The results indicate that E. acicularis has the ability to accumulate Sb, As, Cu, and Zn from contaminated water.     

Behaviour of hexachlorocyclohexane isomers and Zn,Cu and Cd in the freshwater-seawater mixing area

Dissolved and suspended concentrations of hexachlorocyclohexane isomers, α, γ and δ HCH, and Zn, Cu and Cd have been measured in the Napostá Grande stream, located in the Blance Bay area, Argentina, for the purpose of studying the behaviour of these compounds in the freshwater-seawater mixing zone. The aim was to establish the mobilization processes, according to their distribution over the dissolved and suspended forms, in order to obtain a better understanding of their impact on organochlorine and heavy metal levels in the marine environment. It is concluded that the compounds studied are removed from solution by suspended matter which is afterwards precipitated during the freshwater-seawater mixing process. Seawater and surface sediment concentrations of these pollutants for two sampling sites in Blanca Bay, Argentina, are also reported.     

Dynamic,Mechanistic, and Thermodynamic Modeling of Zn(II) Ion Biosorption onto Zinc Sequestering Bacterium VMSDCM

The surface of the bacterial cells before the biosorption of Zn(II) ion has been found rough, heterogeneous, and non‐crystalline together with tremendous protrusions and negatively charged functional groups. The bacterium was characterized as rod shaped with Gram‐negative type of cell wall structure. In reaction dynamics, pseudo‐second‐order kinetics with higher linear correlation coefficient (R²) ranging between 0.97 and 0.99, lower sum of square errors (SSE) (0.035–0.081) and chi (χ²) (0.0013–0.009) provided a better explanation of sorption of Zn(II) ion on bacterium surface as compared to pseudo‐first‐order model. The removal of Zn(II) was governed by both film and intra‐particle diffusion at onset and later stage of sorption of metal ion on the surface of bacterial cells. The R² (0.92–0.94) for intra‐particle diffusion model was quite higher with lower values of SSE (9.56–16.33) and chi (χ²) (11.26–19.65) against the Bangham's model. The positive value of ΔH (16.628 × 10^?6 kJ/mol) and ΔS (5320.90 kJ/mol/K) showed that the biosorption of Zn(II) ion across liquid phase on bacterial surface was endothermic with increased randomness at solid–liquid interface. The negative values of ΔG demarcated the whole process as spontaneous in nature. In the present work, the distribution coefficient was found to be > 0.5 at various temperature ranges. At the attainment of equilibrium, the residual concentration of Zn(II) ion in liquid phase was around 0.6 mg/L, which was much below the limit described by United States Environmental Protection Agency (USEPA), i.e. 5 mg/L.     

Photosynthetic capability and Fe,Mn, Cu,and Zn contents in two Moraceae species under different phosphorus levels

The strong adaptability of Broussonetia papyrifera(L.) Vent. to low phosphorus(P) conditions can be attributed to the large amount of root-exuded organic acids and the high ef?ciency of P extraction. However,microelement contents are in?uenced by low-P stress, and their effects on the photosynthetic capability of B. papyrifera remain unknown. In this study, we investigated the effects of low-P treatment on net photosynthetic rate(P_N);chlorophyll a ?uorescence(ChlF) characteristics; and Fe,Mn, Cu, and Zn contents of B. papyrifera and Morus alba L. seedlings. Results show that B. papyrifera exhibited better photosynthetic capability under moderate P de?-ciency(0.125, 0.063, and 0.031 mmol/L P treatments),whereas the photosynthetic capability of M. alba decreased under moderate and severe P de?ciency(0.016 and0 mmol/L P treatments). Under moderate P de?ciency, the decrease in Cu and Zn contents in B. papyrifera was lower than that in M. alba. Under severe P de?ciency, a considerable decrease of photosynthetic capability in B. papyrifera and M. alba was associated with low Cu and Zn contents. The P N of the two Moraceae species exhibited a better correlation with Cu and Zn contents than with Fe or Mn content. P de?ciency could not only decrease cyclic photophorylation and photosynthetic ef?ciency, but could also affect the stability of thylakoid membrane structure and electron transport ef?ciency by in?uencing the contents of Cu or Zn, thereby affecting photosynthesis.     

Removal of As,Cd, Cu,Ni, Pb,and Zn from a highly contaminated industrial soil using surfactant enhanced soil washing

Surfactant enhanced soil washing (SESW) was applied to an industrial contaminated soil. A preliminary characterization of the soil regarding the alkaline-earth metals, Na, K, Ca and Mg took values of 2866, 2036, 2783 and 4149 mg/kg. The heavy metals As, Cd, Cu, Pb, Ni and Zn, had values of 4019, 14, 35582, 70, 2603, and 261 mg/kg, respectively. When using different surfactants, high removal of Cu, Ni and Zn were found, and medium removals for Pb, As and Cd. In the case of these three metals, tap water removed more than the surfactant solutions, except for the case of As.There were surfactants with average removals (this is, the removal for all the metals studied) of 67.1% (Tween 80), 64.9% (Surfacpol 14104) and 61.2% (Emulgin W600). There were exceptional removals using Texapon N-40 (83.2%, 82.8% and 86.6% for Cu, Ni and Zn), Tween 80 (85.9, 85.4 and 81.5 for Cd, Zn and Cu), Polafix CAPB (79%, 83.2% and 49.7% for Ni, Zn and As). The worst results were obtained with POLAFIX LO with a global removal of 45%, well below of the average removal with tap water (50.2%).All removal efficiencies are reported for a one step washing using 0.5% surfactant solutions, except for the case of mezquite gum, where a 0.1% solution was employed.     

Kinetics,Mechanistic and Thermodynamics of Zn(II) Ion Sorption: A Modeling Approach

Biosorption potential of Cedrus deodara sawdust (CDS) in terms of sorption of Zn(II) ion across liquid phase has been evaluated in the present investigation. The surface of the CDS biomass before the sorption of Zn(II) ions seemed to be more porous, non‐crystalline and heterogeneous. The maximum uptake capacity of CDS was 97.39 mg g^?1. Sorption of Zn(II) ion on the surface of CDS sawdust was maximum at pH 5, temperature 45°C, initial concentration of Zn(II) ion 100 mg L^?1, biomass dose 1 g L^?1, contact time 150 min, and agitation rate 160 rpm. Pseudo second‐order kinetics with the highest linear regression coefficient (R² = 0.99), and lowest values of error functions, i.e., chi (χ²) and sum of square errors (SSE) against pseudo first‐order rate kinetics showed that the sorption of Zn(II) ion on the surface of CDS was mediated by chemosoprtive forces of attraction rather than physical adsorption. Mechanistically, relatively higher proportion of sorption of Zn(II) ion in early phase of contact time was profoundly explained by Bangham's equation and film diffusivity (D^f). Intraparticle or pore diffusion (D_p) of Zn(II) ion inside the pores of CDS was rate limiting step at the later stage of contact time. Furthermore, the thermodynamic study on sorption of metal ion delineated the fact that the Zn(II) sorption on the surface of CDS was spontaneous, endothermic together with increased entropy at solid liquid interface.     

Determination of EC50 Values for Cu,Zn, and Cr on Microorganisms Activity in a Mediterranean Sandy Soil

Ecotoxicity of three potentially toxic metals (PTM) (Cu, Zn, and Cr) in a slightly acidic sandy soil is tested using the soil respiration test (OECD‐217) in order to determine EC₅₀ values for the carbon transformation activity of microorganisms. Addition of an organic amendment of Populus leaves is also crossed with metal spiking in order to investigate possible interaction with metal toxicity. Soil respiration is measured at day 1 and 28 after the soil spiking with the PTM to assess short‐term effects on soil microbial activity. Of the three metals tested, Cu shows the highest toxicity at the longest exposure times (day 28) and Zn shows a strong inhibitory effect in the short‐term (day 1), even though later toxicity diminish significantly. Cr is the least toxic studied PTM. Organic amendment outweighs any adverse effects of these metals, increasing soil respiration, even in the treatments with high doses of metals.     

Zn(II) Ion Biosorption onto Surface of Eucalyptus Leaf Biomass: Isotherm,Kinetic, and Mechanistic Modeling

Bioremediation of Zn(II) by biosorption across aqueous phase on to surface of eucalyptus leaf powder has been investigated in present research work. The adsorptive potential of eucalyptus leaf powder was evaluated as function of pH, temperature, contact time, agitation rate and particle size. Maximum metal ion uptake and percentage removal capacity of eucalyptus leaf powder were 23.5 mg g⁻¹ and 94%, respectively, at optimized pH 5, 20 ± 1°C, contact time 6 h, particle size 0.5 mm and agitation rate 200 rpm. The biomass surface analysis revealed the fact that the biomass surface was heterogeneous and porous in nature. The functional groups like amine, amide, carboxyl, hydroxyl, and methyl groups, significantly important for metal ion binding were present on biomass surface in tremendous amount. Additionally, the Fourier transformation IR spectrum analysis of acid and base activated eucalyptus leaf biomass ruled out all the possibilities of the presence of surface functional groups mentioned above. The reaction rate was studied by applying two rate limiting models pseudo first and pseudo second order. Pseudo second order model was found to be more suitable (R² = 0.998) in comparison to pseudo first order (R² = 0.724). Adsorption equilibrium of batch stirred reaction data fitting shows the dominance of Langmuir isotherm (R² = 0.99) against Freundlich isotherm (R² = 0.887) model with equipartitional involvement of both film and intra particle diffusion as rate limiting steps at differential status of contact time.     

Metal speciation (Cu, Zn, Pb) and organic matter in an oxic salt marsh, Severn Estuary, southwest Britain

Predominantly anthropogenic Cu, Zn, and Pb present in an approximately 100 yr old mud flat and salt marsh deposit at a high intertidal, oxic site are bound chiefly in the Fe---Mn oxide-hydroxide, organic and residual phases. The amount of each metal in the organic phase is significant and declines with increase in the age of the buried sediment, in harmony with the total amount of organic matter remaining. Application of a quantitative geochemical model provides evidence that those metals remobilized by the progressive oxic degradation of the organic matter do not swell the oxide phase also present in the deposit, but are free to be flushed back into the estuary.     

Chemical forms of Pb, Zn and Cu in the sediment profiles of the Pearl River Estuary

The chemical forms of heavy metals (Pb, Zn and Cu) in sediment cores of the Pearl River Estuary were studied using a sequential chemical extraction method. The isotope ratios of 206Pb/207Pb in various chemical fractions were also measured to assess the potential Pb sources. Zinc and Cu were mainly associated with the residual fraction. The Fe-Mn oxide and organic/sulphide fractions were the next important phases for Zn and Cu, respectively. For Pb, different chemical partitioning patterns were found among different sediment cores. Most Pb was associated with the residual fraction in the sediments. In some sediment profiles, the major phase of Pb in the top layers was the Fe-Mn oxide fraction. The proportion of Pb in the Fe-Mn oxide fraction decreased significantly with increasing depth. Among the different depths, the 206Pb/207Pb isotope ratios in the residual fraction remained fairly stable, with a mean value of 1.202, which may represent the natural background value. The 206Pb/207Pb ratios in the exchangeable fraction were the lowest among the five fractions, particularly in top sediments, showing the anthropogenic inputs of heavy metals from recent rapid industrial development in the surrounding region. For the other three non-residual fractions, there was a similar trend of increasing 206Pb/207Pb ratios down the profile. Results from this study are useful in assessing both the chemical changes for heavy metals in marine sediments and the potential of heavy metal release into the water environment of an estuary area.     

Flocculation,heavy metals (Cu,Pb, Zn) and the sand–mud transition on the Adriatic continental shelf,Italy

Across a limited depth range (5–10 m) on many continental shelves, the dominant sediment size changes from sand to mud. This important boundary, called the sand–mud transition (SMT), separates distinct benthic habitats, causes a significant change in acoustic backscatter, represents a key facies change, and delimits more surface-reactive mud from less surface-reactive sand. With the goal of improving dynamical understanding of the SMT, surficial sediments were characterized across two SMTs on the Adriatic continental shelf of Italy. Geometric mean diameter, specific surface area (SSA), mud fraction (<63 μm) and heavy metal concentrations were all measured. The SMT related to the Tronto River is identified between 15 and 20 m water depth while the SMT associated with the Pescara River varies between 15 and 25 m water depth. The sediment properties correlate with a new, process-based sedimentological parameter that quantifies the fraction of the sediment in the seabed that was delivered as flocs. These correlations suggest that floc dynamics exert strong influence over sediment textural properties and metal concentrations. Relative constancy in the depth of the SMT along this portion of the margin and its lack of evolution over a period during which sediment input to the margin has dramatically decreased suggest that on the Adriatic continental shelf energy is the dominant control on the depth of the SMT.     

A laboratory study of the biogeochemical cycling of Fe,Mn, Zn and Cu across the sediment-water interface of a productive lake

Laboratory incubation experiments were carried out on sediment cores collected from Esthwaite Water, U.K., during April 1987, when the sediments displayed a characteristic surface (1.5 to 2 cm) oxide floc. The experiments were undertaken at 10°C, in the dark, under variable redox and pH conditions for periods of ~ 720 h (30 d). In some cases, realistic amounts of decomposing lake algae were added to simulate the deposition of an algal bloom. Pore waters and overlying waters were obtained from the incubated sediment cores at various time intervals and the samples analysed for pH and dissolved Fe, Mn, Zn and Cu by AAS. The results demonstrated that trace metal concentrations at the sediment-water interface can show rapid, pulsed responses to episodic events associated with controlling factors such as algal deposition and mixing conditions. The variations in dissolved Fe and Mn concentrations could generally be explained by their well known redox behaviour. Appreciable loss of Mn from solution under conditions of well-developed anoxia was consistent with adsorption of Mn²⁺ by FeS. Cu and Zn were both rapidly (24 h) released into solution during incubation of sediment cores prior to the development of anoxia in the overlying waters. Their most likely sources were the reductive remobilization of Mn oxides and the decomposition of organic matter. The addition of decomposing algae to a series of cores resulted in even higher interfacial dissolved concentrations of Cu and Zn, probably through acting as a supplementary source of the metals and through increased oxide dissolution. Switching from anoxic to oxic conditions also rapidly increased dissolved Cu and Zn concentrations, possibly due to their release during the oxidation of metal sulphides. The enhanced releases of dissolved Cu and Zn were generally short-lived with removal being attributed to the formation of sulphides during anoxia and to adsorption by Fe and Mn oxides under oxic conditions.