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.     

Micellar-enhanced ultrafiltration (MEUF) with mixed surfactants for removing Cu(II) ions

A nonionic surfactant, polyoxyethylene Octyl phenyl ether (Triton-X), is added to a micellar-enhanced ultrafiltration process to lower the critical micellar concentration (CMC) of an anionic surfactant, sodium dodecyl sulfate (SDS). The effects of adding Triton-X on the copper removal efficiency, the permeate SDS concentration, the copper binding capacity of SDS micelles, and membrane fouling are investigated. Our results show that the addition of Triton-X at concentrations greater than its CMC can reduce the SDS dosage required for effective Cu removal, and at the same time, minimize the permeate SDS concentration. Although, no adverse effect on the copper binding capacity of SDS micelle is observed by the addition of Triton-X, the membrane fouling is worsen. Cleaning the membrane with DI water allowed restoring the membrane flux, indicating that the fouling caused by Triton-X was reversible.     

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.     

Chemical indicators of anthropogenic impacts in sediments of the pristine karst lakes

The anthropogenic impact on the pristine karst lakes was investigated using combination of specific parameters, including multielemental analysis of major inorganic constituents (Al, K, Fe) and trace metals (Li, Ag, Cd, Sn, Pb, Bi, Cr, Co, Ni, Cu, Zn and Sb), polycyclic aromatic hydrocarbons (PAHs) and anionic surfactants of linear alkylbenzene sulfonate (LAS) type. The study was performed in the Plitvice Lakes National Park, situated in a sparsely populated area of the northwestern Dinarides, central Croatia. Dated cores of recent sediments from the two biggest lakes, Lake Prosce and Lake Kozjak, were analysed for the selected contaminants using highly specific methods, involving inductively coupled plasma mass spectrometry (ICP/MS), gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). The concentration of inorganic constituents reflected primarily the geological background of the area as well as geomorphological and geochemical characteristics of the Plitvice Lakes. Due to the higher terrigenous input, the concentration of all elements was significantly higher in the Lake Prosce. The concentration of toxic metals was relatively low in both lakes, except for Cd (>1 mg kg⁻¹) and Pb (up to 40 mg kg⁻¹). The vertical profiles of these metals suggested that elevated concentrations of Cd were of natural origin, derived from the erosion of the Jurassic dolomite bedrock, while Pb was predominately of recent anthropogenic origin. A similar distribution pattern, suggesting the same prevailing mechanism of input, was observed for pyrolytic PAHs. The characteristic diagnostic PAH ratios revealed that higher PAHs prevailingly originated from the combustion of biomass and fossil fuels. LAS, which represent highly specific indicators of untreated wastewaters, were found in rather high concentrations in the recent sediment layers (up to 4.7 mg kg⁻¹), suggesting that contaminated household and hotel wastewaters reach the Lakes, very probably by leaking through the porous karst rocks.     

Metal accumulation in the greentail prawn, Metapenaeus bennettae, in Sydney and Port Hacking estuaries, Australia

Metal concentrations of the inshore greentail prawn, Metapenaeus bennettae, and surface sediments from locations within Sydney estuary and Port Hacking (Australia) were assessed for bioaccumulation and contamination. The current study aimed to assess metal concentrations in prawn tissue (tail muscle, exoskeleton, hepatopancreas and gills), relate whole body prawn tissue metal concentrations to sediment metal concentrations and animal size, as well as assess prawn consumption as a risk to human health. Metal concentrations were highest in sediment and prawns from contaminated locations (Iron Cove, Hen and Chicken Bay and Lane Cove) in Sydney estuary compared with the reference estuary (Port Hacking). Concentrations in sediments varied considerably between sites and between metals (As, Cd, Cr, Cu, Ni, Pb and Zn), and although concentrations exceeded Interim Sediment Quality Guideline-Low values, metals (As, Cd, Cr, Cu, Ni, Pb and Zn) were below Australian National Health and Medical Research Council human consumption guidelines in prawn tail muscle tissue. Metal concentrations in prawn tail muscle tissue were significantly different (p?≤?0.05) amongst locations for Pb, Zn and Cd, and metal concentrations were generally highest in gills tissue, followed by the hepatopancreas, exoskeleton and tail muscle. The exoskeleton contained the highest Sr concentration; the hepatopancreas contained the highest As, Cu and Mo concentrations; and the gills contained the highest Al, Cr, Fe and Pb concentrations. Concentrations of Pb, As and Sr were significantly different (p?≤?0.05) between size groups amongst locations.     

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.     

Heavy metal sources identification and sampling uncertainty analysis in a field-scale vegetable soil of Hangzhou, China

At a field-scale (6.7 ha), 100 surface soil samples were collected from a vegetable field to determine total concentrations of Cd, Co, Cu, Hg, Mn, Ni and Zn. To identify possible sources of these metals and characterize their spatial variation, classic statistic and geostatistic techniques were applied. Through correlation and geostatistical analysis, it was found that the primary inputs of Co, Mn and Ni were due to pedogenic sources, whereas the sources of Hg and Cd were mainly due to human activities. Because of their different sources, their variations followed: Hg > Cd ≈ Cu > Zn ≈ Co ≈ Mn ≈ Ni. Based on their relationships with other soil properties, co-kriging was used to minimize sampling density. Sampling numbers for Cd, Cu, Zn, Mn, Co and Ni can be reduced from 100 to 90, 80, 70, 60, 60 and 60, respectively, without losing accuracy relative to ordinary kriging.     

Simulating the long-term chemistry of an upland UK catchment: heavy metals

CHUM-AM was used to investigate the behaviours of atmospherically-deposited heavy metals (Ni, Cu, Zn, Cd and Pb) in three moorland sub-catchments in Cumbria UK. The principal processes controlling cationic metals are competitive partitioning to soil organic matter, chemical interactions in solution, and chemical weathering. Metal deposition histories were generated by combining measured data for the last 30 years with local lake sediment records. For Ni, Cu, Zn and Cd, default parameters for the interactions with organic matter provided reasonable agreement between simulated and observed present-day soil metal pools and average streamwater concentrations. However, for Pb, the soil binding affinity in the model had to be increased to match the observations. Simulations suggest that weakly-sorbing metals (Ni, Zn, Cd) will respond on timescales of decades to centuries to changes in metal inputs or acidification status. More strongly-sorbing metals (Cu, Pb) will respond over centuries to millennia.     

Relationship between heavy metals concentrations in egret species,their environment and food chain differences from two Headworks of Pakistan

Concentration of ten metals (Cd, Cr, Co, Cu, Fe, Li, Mn, Ni, Pb and Zn) were analyzed in the egg contents, prey and soil samples of little egret (Egretta garzetta) and cattle egret (Bubulcus ibis) from two Headworks to determine habitat and species-specific differences; to assess the importance of prey and habitat contamination as an exposure source for heavy metals. Concentration of Cu, Mn, Cr and Pb in egg contents, Fe, Co, Cu, Mn, Zn in prey and Fe, Co, Cu, Ni, Li in surface soils were significantly different (P < 0.05). Mean metal concentrations of Cr, Pb and Cd were relatively higher in little egret whereas Cu and Mn were higher in the egg contents of cattle egret. The mean concentrations of Cu, Mn and Zn were higher in prey samples of cattle egrets and Cr, Cd and Pb in prey samples of little egrets. In soil samples collected from little egret heronries metal concentrations were higher except Cu and Ni. Correlation Analysis and Hierarchical Agglomerative Cluster Analysis (HACA) identified relatively similar associations of metals and their source identification. Metals such as Fe, Cu, Mn, and Li were related with geochemical origin from parent rock material as well as anthropogenic input whereas Cr, Cd, Pb, Ni, Co and Zn were associated mostly with anthropogenic activities. The study suggested that eggs are useful bio-monitor of local heavy metal contamination.     

Resuspension of contaminated field and formulated reference sediments Part I: Evaluation of metal release under controlled laboratory conditions

In aquatic systems where metal contaminated sediments are present, the potential exists for metals to be released to the water column when sediment resuspension occurs. The release and partitioning behavior of sediment-bound heavy metals is not well understood during resuspension events. In this study, the release of Cd, Cu, Hg, Ni, Pb and Zn from sediments during resuspension was evaluated using reference sediments with known physical and chemical properties. Sediment treatments with varying quantities of acid volatile sulfide (AVS), total organic carbon (TOC), and different grain size distributions were resuspended under controlled conditions to evaluate their respective effects on dissolved metal concentrations. AVS had the greatest effect on limiting release of dissolved metals, followed by grain size and TOC. Predictions of dissolved concentrations of Cd, Ni, Pb and Zn were developed based on the formulated sediment Σ_metal/AVS ratios with Σ_metal being the total sediment metal concentration. Predicted values were compared to measured dissolved metal concentrations in contaminated field sediments resuspended under identical operating conditions. Metal concentrations released from the field sediments were low overall, in most cases lower than predicted values, reflecting the importance of other binding phases. Overall, results indicate that for sulfidic sediments, low levels of the study metals are released to the dissolved phase during short-term resuspension.     

Mechanisms of enhanced mobilisation of trace metals by anionic surfactants in soil

Long-term applications of small concentrations of surfactants in soil via wastewater irrigation or pesticide application may enhance trace metal solubility. Mechanisms by which anionic surfactants (Aerosol 22, SDS and Biopower) affect trace metal solubility were assessed using batch, incubation and column experiments. In batch experiments on seven soils, the concentrations of Cu, Cd, Ni and Zn in the dissolved fraction of soils increased up to 100-fold at the high application rates, but increased less than 1.5-fold below the critical micelle concentration. Dissolved metal concentrations were less than 20% affected by surfactants in long-term incubations (70 days) up to the largest dose of 200 mg C kg⁻¹ soil. Leaching soil columns with A22 (100-1000 mg C L⁻¹) under unsaturated conditions increased trace metal concentrations in the leachates 2-4 fold over the control. Correlation analysis and speciation modelling showed that the increased solubility of metals upon surfactant application was more related to the solubilisation of soil organic matter from soil than to complexation of the metals with the surfactant. Organic matter from soil was solubilised in response to a decrease of solution Ca²⁺ as a result of Ca-surfactant precipitation. At environmentally relevant concentrations, surfactant application is unlikely to have a significant effect on trace metal mobility.     

Trace metals in surface sediments of the Taiwan Strait: geochemical characteristics and environmental indication

The concentration and geochemical fractionation of six trace metals related with environmental quality assessment, namely Cd, Cr, Cu, Ni, Pb, and Zn, in 30 surface sediments from both inshore and offshore areas of the Taiwan Strait were measured to investigate their distribution characteristics, evaluate their potential mobility, and assess their pollution status. The geoaccumulation index results indicated that, on average, the studied metals presented an order of Cd?>?Pb?>?Ni?>?Zn?>?Cu?>?Cr and were practically in uncontaminated status except Cd. The results of the sequential extraction analysis indicated that, on average, the studied metals were mostly accumulated in residual fraction except Cd whose concentration was the highest in the acid soluble fraction presenting a high risk to the environment, and their mobility decreased in the sequence of Cd?>?Pb?>?Ni?>?Cu?>?Zn?>?Cr. Based on the mean probable effect level quotients, the combination of the studied metals had an 8 % probability of being toxic at two sampling sites and had a 21 % probability of being toxic at the rest of sites. The spatial distribution of the studied metals in total concentrations and different geochemical fractions corroborated the previous findings about the possible sediment transportation routes in and around the Taiwan Strait.     

Influence of the presence of heavy metals and surface-active compounds on the sorption of bisphenol A to sediment

The effects of different heavy metals (Cd, Pb), cationic surfactants cetyltrimethylammonium bromide (CTAB), anionic surfactant sodium dodecylbenzenesulfonate (SDBS) and the chemistry of the solution (pH and ionic strength) on the sorption of bisphenol A (BPA) to sediment were studied. Results showed that the presence of Cd and Pb caused a significant increase on the sorption of BPA to sediment and the sorption isotherms were in good agreement with Freundlich equation. The effect of surfactants on the adsorption of BPA onto sediment was found to strongly depend on the type of the surfactants. The presence of CTAB promoted BPA sorption and the amount of BPA adsorbed onto sediment increased linearly with concentration of CTAB. In contrast, the presence of anionic surfactant (SDBS) caused a slight reduction on the sorption of BPA. It was also found that the sorption behavior of BPA was affected by solution pH and ionic strength. The larger amount of BPA was absorbed with higher ionic strength and lower pH. This study may provide important insights into the understanding of the transport and fate of BPA in the environment.     

Assessment of heavy metal contamination in Hindon River sediments: a chemometric and geochemical approach

The aim of this study was to assess the level of heavy metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in the surface sediments of the Hindon River, India that receives both treated and untreated municipal and industrial discharges generated in and around Ghaziabad, India. Mean metals concentrations (mg kg⁻¹) were in the range of; Cu: 21.70-280.33, Cd: 0.29-6.29, Fe: 4151.75-17318.75, Zn: 22.22.50-288.29, Ni: 13.90-57.66, Mn: 49.55-516.97, Cr: 17.48-33.70 and Pb: 27.56-313.57 respectively. Chemometric analysis was applied to identify contribution sources by heavy metals while geochemical approaches (enrichment factor and geo-accumulation index) were exploited for the assessment of the enrichment and contamination level of heavy metals in the river sediments. Chemometric analysis suggested anthropic origin of Cu, Cd, Pb, Zn, and Ni while Fe showed lithogenic origin. Mn and Cr was associated and controlled by mixed origin. Geochemical approach confirms the anthropogenic influence of heavy metal pollution in the river sediments. The study suggests that a complementary approach that integrates chemometric analysis, sediment quality criteria, and geochemical investigation should be considered in order to provide a more accurate appraisal of the heavy metal pollution in river sediments. Consequently, it may serve to undertake and design effective strategies and remedial measures to prevent further deterioration of the river ecosystem in future.     

Metal concentrations and mobility in marine sediment and groundwater in coastal reclamation areas: a case study in Shenzhen, China

The concentrations of metals in the buried marine sediment and groundwater were differently affected by land reclamation. Nine metals (V, Cr, Mn, Co, Ni, Cu, Zn, Cd and Pb) in sediment and coastal groundwater from reclamation areas in Shenzhen were examined. The gradually decreased concentrations (V, Cr, Mn, Ni, Cu, Zn) in sediment and relatively higher concentrations (V, Cr, Mn, Co, Ni, Cu and Cd) in groundwater within reclamation areas were observed. The increase of V, Cr, Mn, Ni, Cu and Cd concentrations in groundwater within reclamation areas subsequently after land reclamation should be resulted from the mobilization of these metals accumulated in the sediment. These metals appear to be easily mobilized from solid phase to solution phase after reclamation. The physico-chemical changes such as reduction in pH and salinity in water environment induced by land reclamation appear to be responsible for metal mobility in the sediment-groundwater system.     

Heavy metal contamination in surface sediments of Yangtze River intertidal zone: An assessment from different indexes

Surface sediments (0-5 cm) from 59 stations within the Yangtze River intertidal zone (YRIZ) were sampled for metal contamination analysis in April and August 2005. The concentrations ranged (in mg kg⁻¹ dry weight): Al, 40,803-97,213; Fe, 20,538-49,627; Cd, 0.12-0.75; Cr, 36.9-173; Cu, 6.87-49.7; Mn, 413-1,112; Ni, 17.6-48.0; Pb, 18.3-44.1; and Zn, 47.6-154; respectively. Among the 59 sampling stations, enrichment factors (EF) indicate enrichment of Cd (52 stations), Cr (54 stations), Cu (5 stations), Ni (26 stations), Pb (5 stations) and Zn (5 stations). Geoaccumulation indexes (I_geo) also suggest individual metal contamination in localized areas. This study indicates that Cd, Cr and Ni enrichment in the YRIZ sediment is widespread whereas Cu, Mn, Pb and Zn enrichment is localized or nonexistent. Factor and cluster analyses indicate that Cd is associated with total organic carbon whereas Cu, Cr, Ni, Pb and Zn have a close association with Mn.     

Availability of heavy metals for uptake by Salix viminalis on a moderately contaminated dredged sediment disposal site

Extractability of Cd, Cr, Cu, Ni, Pb, and Zn in a dredged sediment disposal site was assessed using single extraction procedures (H2O; 0.01 M CaCl2; 1 M NH4OAc; NH4OAc-EDTA; CaCl2-TEA-DTPA). Only Cd and Zn were found to exceed statutory threshold values for total content. The field was planted with Salix viminalis "Orm" and accumulation of heavy metals in bark, leaves, roots, and wood was evaluated at seven sampling locations along an observed gradient in texture and pollution. Biomass production was high, ranging from 13.2 to 17.8 t ha(-1) y(-1) dry weight. Metal accumulation in aboveground plant parts was low, amounting to the following annually extracted mass of metals per ha: 5034 g Zn, 83 g Cd, 145 g Cu, 83 g Pb, 12 g Ni and 6 g Cr. The use of accumulating clones and the use of soil amendments might enhance extraction efficiency in future research.     

Influence of synthetic surfactants on the uptake of Pd, Cd and Pb by the marine macroalga, Ulva lactuca

Uptake of Pd, Cd and Pb by the marine macroalga, Ulva lactuca, has been studied in the presence of an anionic (sodium dodecyl sulphate, SDS), cationic (hexadecyltrimethylammonium bromide; HDTMA) and non-ionic (Triton X-100; TX) surfactant. Compared with the surfactant-free system, metal sorption was reduced in the presence of SDS or TX. Neither surfactant, however, had any measurable impact on cell membrane permeability, determined by leakage of dissolved free amino acids (DFAA), or on metal internalisation. We attribute these observations to the stabilisation of aqueous Cd and Pb by SDS and the shielding of otherwise amenable sorption sites by TX. Presence of HDTMA resulted in a reduction in the extent of both sorption and internalisation of all metals and a significant increase in the leakage of DFAA. Thus, by enhancing membrane permeability, HDTMA exerts the greatest influence on metal behaviour in the presence of U. lactuca.     

Oxidative stress on land snail Helix aspersa as a sentinel organism for ecotoxicological effects of urban pollution with heavy metals

The oxidative stress in the digestive gland of the land snail Helix aspersa was considered as a bioindicator for atmospheric pollution with heavy metals from several industries and vehicular traffic in Kafr El-Zayat city. Regional means of heavy metals concentration of all sites were 0.71, 7.09, 0.71, 2.68, 41.44 and 18.01 mg kg⁻¹ wet mass for Cd, Mn, Ni, Pb, Zn and Cu, respectively. In addition, the highest values of Cd concentrations were found 1.22 and 1.73 mg kg⁻¹ wet mass in S1 (Potato International Center) and S4 (The Nile bank), respectively. Lactate dehydrogenase (D-LDH(and recorded lipid peroxidation (LPO) levels were significantly high in S1 and S2 (Traffic station). On the other hand, the highest activity of catalase (CAT) was found in S2 (194.04% of control), while the activity of glutathione peroxidase (GP_x) reached the highest significant value in S1.