Speciation of Cd and Zn in contaminated soils assessed by DGT-DIFS, and WHAM/Model VI in relation to uptake by spinach and ryegrass

A pot experiment was carried out to investigate the impact of Cd and Zn extractability in soil and speciation in pore water of industrial contaminated soils, on metal concentration in a metal sensitive species like spinach (Spinacia oleracea) and a more metal tolerant species like Italian ryegrass (Lolium multiflorum). For chemical speciation of Cd and Zn in pore water, WHAM/Model VI version 6.0 was used. The DGT technique was used to determine the effective concentration, C(E), of Cd and Zn in soils. The free ion activity in pore water correlated well with the contents in plants, and there was a linear relationship between the C(E) values and the concentration of Cd and Zn in both spinach and ryegrass in the non-toxic range. However, the C(E) values usually overestimated the plant contents when plants, particularly the spinach plants, were subjected to toxic concentration in the pore water. Metal uptake decreased in plants affected by toxicity, whereas metal binding to the Chelex resin did not. Thus, we found no linear relationship between the C(E) and metal contents in spinach, whereas a linear relationship was found between C(E)-Zn and the Zn concentration in ryegrass (r2=0.96, p<0.001). For Cd in ryegrass this relationship was weak (r2=0.53, p=0.18). This study indicates that the transport of metals from labile metal pools to the DGT-resin is linearly related to plant uptake only when plants are growing well, and that the applicability of DGT as an indicator for plant uptake seems species dependent.     

Modelling the extra and intracellular uptake and discharge of heavy metals in Fontinalis antipyretica transplanted along a heavy metal and pH contamination gradient

Samples of the aquatic bryophyte Fontinalis antipyretica Hedw. were transplanted to different sites with the aim of characterizing the kinetics of the uptake and discharge of heavy metals in the extra and intracellular compartments. The accumulation of metals in extracellular compartments, characterized by an initial rapid accumulation, then a gradual slowing down over time, fitted perfectly to a Michaelis-Menten model. The discharge of metals from the same compartment followed an inverse linear model or an inverse Michaelis-Menten model, depending on the metal. In intracellular sites both uptake and discharge occurred more slowly and progressively, following a linear model. We also observed that the acidity of the environment greatly affected metal accumulation in extracellular sites, even when the metals were present at relatively high concentrations, whereas the uptake of metals within cells was much less affected by pH.     

The solid-solution partitioning of heavy metals (Cu,Zn, Cd,Pb) in upland soils of England and Wales

Ninety-eight surface soils were sampled from the uplands of England and Wales, and analysed for loss-on-ignition (LOI), and total and dissolved base cations, Al, Fe, and trace heavy metals (Cu, Zn, Cd, Pb). The samples covered wide ranges of pH (3.4-8.3) and LOI (9-98%). Soil metal contents measured by extraction with 0.43 mol l-1 HNO3 and 0.1 mol l-1 EDTA were very similar, and generally lower than values obtained by extraction with a mixture of concentrated nitric and perchloric acids. Total heavy metal concentrations in soil solution depend positively upon soil metal content and [DOC], and negatively upon pH and LOI, values of r2 ranging from 0.39 (Cu) to 0.81 (Pb). Stronger correlations (r2=0.76-0.95) were obtained by multiple regression analysis involving free metal ion (Cu2+, Zn2+, Cd2+, Pb2+) concentrations calculated with the equilibrium speciation model WHAM/Model VI. The free metal ion concentrations depend positively upon MHNO3 and negatively upon pH and LOI. The data were also analysed by using WHAM/Model VI to describe solid-solution interactions as well as solution speciation; this involved calibrating each soil sample by adjusting the content of "active" humic matter to match the observed soil pH. The calibrated model provided fair predictions of total heavy metal concentrations in soil solution, and predicted free metal ion concentrations were in reasonable agreement with the values obtained from solution-only speciation calculations.     

Speciation of heavy metals in marine sediments vs their bioaccumulation by mussels.

Total contents and speciation of selected heavy metals, including Al, Fe, Co, Ni, Pb, Zn, Cu, Cr, were measured in sediment samples and mussels Mya arenaria and Astarte borealis collected in the Horsund Fjord off Spitsbergen (Norwegian Sea) and the Bay of Gdansk (Baltic Sea). The investigation aimed at revealing differences in the accumulation pattern of heavy metals in mussels inhabiting sediments characterized by varying metal bioavailability. The contents of metals adsorbed to sediments and associated with iron and manganese hydroxides, which were obtained by sequential extraction, were utilized as a measure of metal bioavailability. The contents of Cd, Pb, Zn, Cu and Cr in mussels collected off Spitsbergen were generally lower than those in mussels from the Baltic Sea. In sediments collected off Spitsbergen the bioavailable fraction represented a small proportion (0-3.7% adsorbed metals and 0-11% associated with metals hydroxides) of total heavy metal contents. In sediments from the Baltic Sea the percentages of metals adsorbed and bound to hydroxides were 1-46% and 1-13%, respectively. The differences in bioavailable metal contents measured in sediments were utilized to explain the different contents of metals in mussels collected in the corresponding sites.     

Challenges in understanding the sources of bioaccumulated metals in biota inhabiting turbid river systems

Bioaccumulation of As, Cd, Cu, Pb and Zn by Macrobrachium prawns was observed to occur in the Strickland River downstream of a gold mine at Porgera, Papua New Guinea. This was despite the total metal concentrations of waters and sediments indicating no difference from reference sites within tributaries. To provide information on potential sources and bioavailability of metals to prawns, an extensive range of analyses were made on waters, suspended solids, deposited sediments and plant materials within the river system. Dissolved metal concentrations were mostly sub-micrograms per liter and no major differences existed in concentrations or speciation between sites within the Strickland River or its tributaries. Similarly, no differences were detected between sites for total or dilute acid-extractable metal concentrations in bed sediments and plant materials, which may be ingested by the prawns. However, the rivers in this region are highly turbid and the dilute acid-extractable cadmium and zinc concentrations in suspended solids were greater at sites in the Strickland River than at sites in tributaries. The results indicated that mine-derived inputs increased the proportion of these forms of metals or metalloids in the Strickland River. These less strongly bound metals and metalloids would be more bioavailable to the prawns via the dietary pathway. The results highlighted many of the difficulties in using routine monitoring data without information on metal speciation to describe metal uptake and predict potential effects when concentrations are low and similar to background. The study indicated that the monitoring of contaminant concentrations in organisms that integrate the exposure from multiple exposure routes and durations may often be more effective for detecting impacts than intermittent monitoring of contaminants in waters and sediments.     

Accumulation of aluminum and iron by bryophytes in streams affected by acid-mine drainage

Accumulation of two heavy metals (Al and Fe) by bryophytes was examined in a northern Pennsylvania stream system affected by acid-mine drainage. Four sites within one watershed were selected on the basis of their pH and dissolved metal concentrations. Significant differences among sites were found with regard to bioaccumulation of Al and Fe. A negative relationship between pH and Fe concentrations in bryophyte tissues was found, with the highest accumulation of Fe observed at the most acidic site (pH 3.5), whereas accumulation of Al was highest at a site with an intermediate pH of 5.2. Bryophytes transplanted from a circum-neutral site to acidic sites showed highly significant increases in Fe and Al concentrations in tissues after 6 weeks, and transplants from more acidic sites to a circum-neutral site generally showed highly significant declines in Fe and Al concentrations in tissues after the incubation period.     

Heavy metal pollution status in surface sediments of Swan Lake lagoon and Rongcheng Bay in the northern Yellow Sea

The national ‘Shandong Peninsula Blue Economic Zone Development Plan’ compels the further understanding of the distribution and potential risk of metals pollution in the east coast of China, where the rapid economic and urban development have been taken off and metal pollution has become a noticeable problem. Surface sediments collected from the largest swan habitat in Asia, the Swan Lake lagoon and the surrounding coastal area in Rongcheng Bay in northern Yellow Sea, were analyzed for the total metal concentrations and chemical phase partitioning of five heavy metals (Cu, Zn, Pb, Cd, and Cr). Metal contents in the studied region have increased significantly in the past decade. The speciation analyzed by the sequential extraction showed that Zn and Cr were present dominantly in the residual fraction and thus of low bioavailability, while Cd, Pb and Cu were found mostly in the non-residual fraction thus of high potential availability, indicating significant anthropogenic sources. Among the five metals, Cd is the most outstanding pollutant and presents high risk, and half of the surface sediments in the studied region had a 21% probability of toxicity based on the mean Effect Range-Median Quotient. At some stations with comparable total metal contents, remarkably different non-residual fraction portions were determined, pointing out that site-specific risk assessment integrating speciation is crucial for better management practices of coastal sediments.     

北运河沉积物/水界面上重金属迁移转化规律

分析测定了6种元素(Cr、Co、Mn、Cu、Pb、Zn)在北运河水系10个采样点水体和表层沉积物中的含量和形态分布,利用SPSS 19.0统计软件对重金属在不同形态中的含量进行相关性分析。结果显示,北运河下游重金属污染程度高于上游;Cr、Cu、Pb、Zn在底泥可提取态中所占比例相当高,多数采样点都超过10.0%。所研究的重金属多数在底泥Fe-Mn结合态与悬浮物、可交换态、硫化物和有机质结合态均存在相关性;Mn是北运河地化循环中最为活跃的元素。     

Competition between alga (Pseudokirchneriella subcapitata), humic substances and EDTA for Cd and Zn control in the algal assay procedure (AAP) medium

The chemical speciation of trace metals in natural waters has important implications for their biogeochemical behavior. Trace metals are present in natural waters as dissolved species and associated with colloids and particles. The complexation of one trace metal (Cd and Zn at 200 and 390 microg/l respectively) with a green alga Pseudokirchneriella subcapitata in colloid-free algal culture medium and in presence of colloidal humic substances (HS) is presented. The influence of the nature of colloids was also addressed using three "standard" HS: fulvic acid (FA) and, soil (SHA) and peat humic acids (PHA). The chemical speciation model, MINTEQA2, was used to simulate the influence of pH and standardized culture medium on metal association with humic substances. The model was successfully modified to consider the differences in the metal complexation with fulvic (FA) and humic acids (HA). The deviations of concentrations of metals associated with HS between experimental results and model predictions were within a factor of approximately 2. The results of speciation model highlight the influence of the experimental conditions (pH, EDTA) used for alga bioassay on the behavior of Cd and Zn. The computed speciation suggests working with a pH buffered/EDTA-free mixture to avoid undesirable competition effects. The behavior of Cd and Zn in solution is more strongly influenced by HS than by alga. Metal-HS associations depend on metal and humic substance nature and concentration. Cd is complexed to a higher extent than Zn, in particular at larger HS concentration, and the complexation strength is in the order FA相似文献   

Evolution of heavy metal speciation during the aerobic composting process of sewage sludge

The contents of heavy metals and their bioavailability to the soil-plant system were the major limitation to the application of sewage sludge compost in soil. This study was conducted to determine the evolution of heavy metal speciation in the course of an aerobic composting, and investigate the influence of changes of composting process parameters including pH, temperature and organic matter (OM) content on distribution of heavy metal speciation in composted sludge. The sequential extraction procedure developed by Tessier et al. was used in sludge compost to determine the heavy metal speciation. Results showed that, during composting, (1) the contents of the residue fraction for Pb, Zn and Cd were decreased but those for Ni and Cr were increased; the Cu residue fraction was almost constant; (2) the contents of the total mobile fractions (including fractions 1-4) for Zn and Pb were significantly increased, but the increase of those for Cu and Ni were not so remarkable; (3) there were significant degrees of correlation between heavy metal fractions and changes of some selected parameters (for example, pH, composting temperature, and OM content). Only the content of the total mobile fractions for Cu could be predictable from its total content. For the prediction of the total mobile fractions of Zn, Ni, Cd and Cr, the R(2) value was significantly increased by the inclusion of other variables such as pH, temperature and OM content.     

Speciation distribution and mass balance of copper and zinc in urban rain, sediments, and road runoff

Heavy metal pollution in road runoff had caused widespread concern since the last century. However, there are little references on metal speciation in multiple environmental media (e.g., rain, road sediments, and road runoff). Our research targeted the investigation of metal speciation in rain, road sediments, and runoff; the analysis of speciation variation and mass balance of metals among rain, road sediments, and runoff; the selection of main factors by principal component analysis (PCA); and the establishment of equation to evaluate the impact of rain and road sediments to metals in road runoff. Sequential extraction procedure contains five steps for the chemical fractionation of metals. Flame atomic absorption spectrometry (Shimadzu, AA-6800) was used to determine metal speciation concentration, as well as the total and dissolved fractions. The dissolved fractions for both Cu and Zn were dominant in rain. The speciation distribution of Zn was different from that of Cu in road sediments, while speciation distribution of Zn is similar to that of Cu in runoff. The bound to carbonates for both Cu and Zn in road sediments were prone to be dissolved by rain. The levels of Cu and Zn in runoff were not obviously influenced by rain, but significantly influenced by road sediments. The masses for both Cu and Zn among rain, road sediments, and road runoff approximately meet the mass balance equation for all rainfall patterns. Five principal factors were selected for metal regression equation based on PCA, including rainfall, average rainfall intensity, antecedent dry periods, total suspended particles, and temperature. The established regression equations could be used to predict the effect of road runoff on receiving environments.     

Study of metal concentrations in the environment near diesel transport routes

In recent years, a river-dredging project has been executed in Nantou, Taiwan. A large number of diesel vehicles carrying gravel and sand shuttle back and forth on the main traffic roads (Tai-16 and Tai-21). The purpose of this study is to figure out the levels of metals contributed by those vehicles to the surrounding environment. Eight stations along the roadside of diesel transport routes were selected as exposure sites, while a small village located about 9 km away from the diesel transport routes was selected as the control site. The mass concentrations of coarse and fine particulate matter indicated that contributions from traffic fleets resulted in a higher percentage of coarse particulate matter in the ambient air at exposure sites in comparison with that at control site. Significantly higher values of EC (elemental carbon) concentrations and ratios of EC/OC (organic carbon) at exposure sites indicate that diesel vehicles at exposure sites contributed a greater amount of pollutants than gasoline vehicles. Exposure site concentrations for all metals measured (Fe, Al, Mn, Pb, Zn, Cu, Ni, Mo and As) for fine and coarse particulate matter were all higher than those at the control site. Recorded levels of metal contents in road dust and riverside soil near Tai-16 and Tai-21 showed that while the traffic fleet did not increase the metal contents of crustal elements in the road dust, it did significantly increase the metal contents of traffic-related elements. Enrichment factors (EFs) were calculated with respect to road dust (EF_road) and with respect to the samples of riverside soil (EF_river). Among these metals, Mo was the most highly-enriched metal. The extremely high EF_river value (4300) of Mo indicates that these stations were highly polluted by diesel emission. Whereas the significantly high EF_road value (810) of Mo implies that a considerable of Mo was emitted from tailpipe of diesel vehicles.     

Ionic strength effects in biosorption of metals by marine algae

Biosorption, the passive accumulation of metals by biomass, can be used as a cost-effective process for the treatment of metal polluted industrial effluents. The green alga Ulva fascia and the brown seaweeds Sargassum hemiphyllum, Petalonia fascia, and Colpomenia sinuosa were characterized in terms of their number of binding sites, their charge density and intrinsic proton binding constant (pKa) using pH titrations at different ionic strengths. The determined number of binding sites decreased in the order Petalonia > or = Sargassum > Colpomenia > Ulva. Due to their high number of binding sites Sargassum and Petalonia are most promising for biosorption applications. The decrease of proton binding with increasing ionic strength and pH as well as the increase of Cu and Ni binding with increasing pH and decreasing ionic strength could be described by the Donnan model in conjunction with an ion exchange biosorption isotherm.     

Solid phase speciation of arsenic by sequential extraction in standard reference materials and industrially contaminated soil samples

Availability, mobility, (phyto)toxicity and potential risk of contaminants is strongly affected by the manner of appearance of elements, the so-called speciation. Operational fractionation methods like sequential extractions have been applied for a long time to determine the solid phase speciation of heavy metals since direct determination of specific chemical compounds can not always be easily achieved. The three-step sequential extraction scheme recommended by the BCR and two extraction schemes based on the phosphorus-like protocol proposed by Manful (1992, Occurrence and Ecochemical Behaviours of Arsenic in a Goldsmelter Impacted Area in Ghana, PhD dissertation, at the RUG) were applied to four standard reference materials (SRM) and to a batch of samples from industrially contaminated sites, heavily contaminated with arsenic and heavy metals. The SRM 2710 (Montana soil) was found to be the most useful reference material for metal (Mn, Cu, Zn, As, Cd and Pb) fractionation using the BCR sequential extraction procedure. Two sequential extraction schemes were developed and compared for arsenic with the aim to establish a better fractionation and recovery rate than the BCR-scheme for this element in the SRM samples. The major part of arsenic was released from the heavily contaminated samples after NaOH-extraction. Inferior extraction variability and recovery in the heavily contaminated samples compared to SRMs could be mainly contributed to subsample heterogeneity.     

PCBs and DDT in the serum of juvenile California sea lions: associations with vitamins A and E and thyroid hormones

In order to better understand the fate of metals during the biodegradation of organic matter in soils, an in vitro incubation experiment was conducted with metal-rich and metal-free leaves of Arabidopsis halleri introduced in a non-contaminated soil. During incubation of these microcosms, we followed the partitioning of Zn and Cd between the solution and their solid components, by determining the metal contents of six soil fractions and dissolved metals after granulo-densimetric separations at selected times. Microbial biomass and exchangeable metals in K(2)SO(4) solutions were also determined at the same times, and two main stages were identified. The first one takes place after a fast abiotic transfer of Zn and Cd from readily soluble plant tissues onto fine soil constituents, keeping metals away from the liquid phase: during about 14 days, microbial biomass increased as well as metal contents of some soil fractions, particularly those rich in particulate organic matter. During the second stage, between 14 and 60 days and for the metal-rich microcosms, Zn and Cd contents in solution increased, while microbial biomass decreased instead of staying constant as in control. A change of Zn and Cd speciation is assumed, from non-toxic adsorbed forms to more toxic species in solution. Remaining metal-rich plant residues seem to create a stable organic C compartment in the soil.     

Interactions of metals affect their distribution in tissues of Phragmites australis

Culms of Phragmites australis were grown in vermiculite in a greenhouse. Some plants were exposed to 1000 microg/g Cu or Pb or Zn, or combinations of two or three of those metals. When plants reached senescence, they were harvested and analyzed for metal concentrations in upper leaves, lower leaves, stems and roots. While all metals accumulated in highest concentrations in the roots, Zn accumulated in aboveground tissues far more than the other metals. Furthermore, the concentration of any one metal in the different tissues was affected by the presence of other metals. The amount of copper in upper leaves increased when Zn was also present with the Cu. The amount of Cu in roots was increased in the presence of Pb and/or Zn. The amount of Zn in lower leaves was reduced when Cu was also present along with Zn. Thus, when combinations of metals were present, the distribution of metals was altered. The most important interactions appeared to be of Cu and Zn, which may reflect competition for binding sites on metal-binding proteins.     

Metal accumulation in aquatic macrophytes from southeast Queensland,Australia

To determine the extent of metal accumulation in some aquatic macrophytes from contaminated urban streams in southeast Queensland, plants were sampled from six sites, along with contiguous sediments. In all, 15 different species were collected, the most common genera being Typha (Cattails or Bulrushes) and Persicaria (Knotweeds). Before heavy metal analysis, plants were further separated into various morphological tissues, and five selected samples were separated into various physiological tissues. The cadmium, copper, lead and zinc content of the plants were analysed using flames AAS. In general, plant roots exhibited higher metal concentrations than the contiguous sediments. Of the metals of interest, only for zinc was there a relatively clear pattern of increasing accumulation in aquatic macrophytes with increasing sediment metal concentrations. Comparison between morphological tissues of the sampled plants found that roots consistently presented higher metal concentrations than either the stems or leaves, however unlike previous studies, this investigation revealed no consistent trend of stems accumulating more metals than the leaves. For Typha spp., metal concentrations followed the order of roots > rhizomes > leaves, while for Persicaria spp. the order was roots > leaves > stems. The submerged species Myriophyllum aquaticum accumulated the highest levels of metals overall (e.g. Zn 4300 micrograms g-1 dry weight and Cd 6.5 micrograms g-1), and the emergent macrophytes also exhibited relatively high metal contents in their roots. The leaves of the submerged and floating-leafed species collected contained relatively high quantities of the four metals of interest, compared with the leaves of emergent aquatic macrophytes. In the Typha rhizome and Persicaria stem samples analysed for internal variation in metal content, there was a pattern of increasing metal concentrations towards the external sections of the stem, both for subterranean stems (rhizomes) and above-substrate stems. For Persicaria stems, no clear pattern was observed for cadmium and lead, the two metals investigated that are not required by plants for survival.     

A comparative study on metal sorption by brown seaweed

This study compared the sorption of Ag, Cd, Co, Cd, Mn, Ni, Pb and Zn by a Ca-treated Sargassum biomass at pH 5.0, under low and high ionic strength (IS) conditions. The sorption isotherms of As [As(V)] and Cr [Cr(III) and Cr(VI)] were also determined at low IS. The isotherm data for the eight cationic metals and Cr(III) were well fitted by Langmuir equations. Generally, the maximum metal uptake (Umax) followed: Cr(III) > Pb approximately Cu > Ag approximately Zn approximately Cd > Ni approximately Mn approximately Co > Cr(VI) > As(V) at low IS and Pb > Cu > Co > Mn approximately Cd > Zn approximately Ag > Ni at high IS. As(V) did not bind to the seaweed at pH 5.0. The results indicated that sorption of Pb was not affected by the increasing IS, though the percentage of free Pb ions in the water was greatly reduced as predicted by the speciation model. High IS lowered Umax by 10-36% (except Co and Pb), and lowered the affinity constant of the metal by 33-91% for all cationic metals, as compared to low IS. Moreover, the removal efficiency of the cationic metals and Cr decreased exponentially with initial metal concentrations and was lower at high IS. Ion-exchange was the mechanism responsible for the cationic metal sorption onto the seaweed, and Na ion interfered with the cationic metal binding through electrostatic interaction. In conclusion, this study showed the differential binding capacity of the Sargassm biomass for different metals and oxidation states and the differential effects of IS. According to the present results, Sargassum may be considered a good biosorbent for cationic metals (especially Pb) in both low and high-salt containing wastewater.     

Copper toxicity to Lemna minor modelled using humic acid as a surrogate for the plant root

Humic acids are chemically analogous to plant root cell walls in that their surface sites are principally comprised of carboxylic and phenolic acids which bind both metals and protons. Based on this analogy, we developed a biotic-ligand type of model to predict Cu toxicity to Lemna minor, using particulate humic acid (HA(part)) of the Windermere Humic Aqueous Model (WHAM), and 7d static-renewal exposures with five surface waters and one nutrient media which varied in DOC (1-10 mg L(-1)), pH (6.9-8.7), and water hardness (35-236 mg equivalent CaCO(3)L(-1)). Although the range of waters tested resulted in a 36-fold variation in 50% inhibitory concentration (IC50) values, the calculated concentration of Cu bound to HA(part) using this framework was highly correlated with pooled percent net root elongation (%NRE) (R(2)=0.95). Ten and fifty percent IC values based on [Cu-HA(part)] were additionally within a factor of ±1.5 and ±1.4, respectively, inclusive of 95% confidence limits. This model construct, which defines the free metal ion and the first hydrolysis product (but not metal carbonate complexes) as being bioavailable, provides an alternative means of defining the binding surface in bioavailability models, whereby a heterogeneous mixture of ligands collectively influence root-metal sorption and toxicity.