Trophic transfer of Cd from natural periphyton to the grazing mayfly Centroptilum triangulifer in a life cycle test

In streams, periphyton biofilms are important sinks for trace metals such as cadmium and are primary food sources of many invertebrate consumers. To study Cd trophic transfer, we produced differentially contaminated diets by exposing natural periphyton to environmentally relevant dissolved Cd ranging from 0 to 10 μg L⁻¹ for 6-7 days using a radiotracer approach. On average, periphyton grown during three different seasons bioconcentrated Cd similarly - approximately 1315 (±442) -fold above dissolved concentrations. However, mayfly larvae (Centroptilum triangulifer) raised on these differentially contaminated diets (first instar through adulthood) had significantly higher trophic transfer factors from periphyton grown in Aug and Nov 2008 (4.30 ± 1.55) than from periphyton grown in Jan 2009 (0.85 ± 0.21). This Cd bioaccumulation difference is only partially explained by apparent food quality and subsequent growth differences. Taken together, these results suggest that primary producers at the base of food webs drive metal bioaccumulation by invertebrate grazers.     

Cadmium accumulation and Cd-binding proteins in marine invertebrates--a radiotracer study

Tissue and subcellular accumulation of cadmium were studied in different tissues of three marine invertebrates (blue mussel Mytilus edulis, the tunicate Ciona intestinalis and the sea star Asterias rubens) using radioactive ¹⁰⁹Cd as a tracer. The organisms were exposed to 0.05, 2 and 50 μg Cd l⁻¹ for 21 days. Quantitative data were obtained by dissecting, weighing and subsequently measuring radioactivity in organs and tissues. Differences between each exposure and each tissue with regard to the amount of radioactivity and metallothionein (MT) content were evaluated. Obvious interspecies differences in Cd accumulation were observed, as well as differences between tissues of the three species. The highest concentrations of Cd in all exposure treatments were found in the hepatopancreas of M. edulis and body wall of A. rubens. Taking all treatments into account, Cd accumulation in the tunic of C. intestinalis was high compared to other tissues from this species. Over 60% of Cd was present in the S50 fraction in all treatments in all three species. Metallothionein levels were increased at the highest Cd-exposure in all species and tissues, except in branchial pharynx of C. intestinalis where the highest MT level was reached following exposure to 2 μg Cd l⁻¹. The most surprising finding was that even the lowest Cd exposure concentration (0.05 μg Cd l⁻¹) caused MT induction in pyloric caeca of A. rubens, but there was no dose-dependent increase in MT at higher exposure levels.     

Ni adsorption and Ni-Al LDH precipitation in a sandy aquifer: an experimental and mechanistic modeling study

Mining activities and industries have created nickel (Ni) contaminations in many parts of the world. The objective of this study is to increase our understanding of Ni adsorption and Nickel-Aluminium Layered Double Hydroxide (Ni-Al LDH) precipitation to reduce Ni mobility in a sandy soil aquifer. At pH ≥7.2 both adsorption and Ni-Al LDH precipitation occurred. In batch experiments with the sandy soil up to 70% of oxalate-extractable Al was taken up in LDH formation during 56 days. In a long term column experiment 99% of influent Ni was retained at pH 7.5 due to Ni adsorption (≈34%) and Ni-Al LDH precipitation (≈66%) based on mechanistic reactive transport modeling. The subsequent leaching at pH 6.5 could be largely attributed to desorption. Our results show that even in sandy aquifers with relatively low Al content, Ni-Al LDH precipitation is a promising mechanism to immobilize Ni.     

Cadmium accumulation in and tolerance of rice (Oryza sativa L.) varieties with different rates of radial oxygen loss

Cadmium (Cd) uptake and tolerance were investigated among 20 rice cultivars based on a field experiment (1.2 mg Cd kg⁻¹ in soil) and a soil pot trial (control, 100 mg Cd kg⁻¹), and rates of radial oxygen loss (ROL) were measured under a deoxygenated solution. Significant differences were found among the cultivars in: (1) brown rice Cd concentrations (0.11-0.29 mg kg⁻¹) in a field soil, (2) grain Cd tolerance (34-113%) and concentrations (2.1-6.5 mg kg⁻¹) in a pot trial, and (3) rates of ROL (15-31 mmol O₂ kg⁻¹ root d.w. h⁻¹). Target hazard quotients were calculated for the field experiment to assess potential Cd risk. Significant negative relationships were found between rates of ROL and concentrations of Cd in brown rice or straw under field and greenhouse conditions, indicating that rice cultivars with higher rates of ROL had higher capacities for limiting the transfer of Cd to rice and straw.     

Cadmium accumulation and its effect on the in vitro growth of woody fleabane and mycorrhized white birch

The effect of Cd on woody fleabane (Dittrichia viscosa (L.) Greuter) and white birch (Betula celtiberica Rothm. & Vasc.) was examined. Woody fleabane and white birch were grown in vitro in Murashige, T., Skoog, F., [1962. A revised medium for rapid growth and bioassays with tobacco tissue cultures. Physiol. Plant. 15, 473-479] (MS) plus Cd (10 mg Cd kg(-1)) and except for root length in white birch, plant development was inhibited when Cd was added. Cd accumulation in above-ground tissues showed differences among clones, reaching 1300 and 463 mg Cd kg(-1) dry wt. in selected clones of woody fleabane and white birch, respectively. Tolerance of Paxillus filamentosus (Scop) Fr. to Cd was also examined before mycorrhization. Plants of mycorrhized white birch grown in the presence of Cd had a better development and accumulated more Cd in their shoots than the non-mycorrhized ones. The use of selected clones of woody fleabane and the mycorrhization of white birch enhance extraction efficiency from contaminated soils in phytoremediation programs.     

Changes in arsenic fractionation, bioaccessibility and speciation in organo-arsenical pesticide amended soils as a function of soil aging

Although organoarsenical pesticides are being phased out, sites with high concentrations of organic arsenical residues still exist due to the long-term application of these pesticides. The biotic and abiotic speciation of dimethylarsinic acid (DMA) can result in the formation of inorganic arsenic (As) species. Oxidation state, retention, and thereby persistence, varies according to temporal changes, influencing the availability and toxicity of contaminants. The current greenhouse study aimed at evaluating temporal changes in the oxidation state of As, geochemical partitioning, and bioaccessibility. Four soils with varying physiochemical properties were contaminated with DMA at two concentrations (675 and 1500 mg kg⁻¹ of As). Rice plants were grown for a 6 months period, following which, the soils were allowed to age. The operationally defined forms of As and its bioaccessibility was analyzed at 0, 6 months, 1 year, and 3 years. Changes in oxidation state of As were evaluated immediately after spiking and after 3 years of soil-pesticide equilibration. Results show that geochemical partitioning of As was affected significantly (P < 0.05) by soil type, loading rates, and equilibration time. Arsenic was bound mainly to the poorly-crystalline Fe/Al-oxyhydroxides in the soil. However, these interactions did not affect As bioaccessibility, presumably due to the dissolution of the bound fractions of As in the acidic stomach. While 74-94% of the total bioaccessible As was transformed to As(V), 4-19% was transformed to the more toxic As(III). This study indicates that although aging affected the geochemical partitioning of As in the soil, bioaccesibility was controlled by the gastric pH.     

Mobility of arsenic, cadmium and zinc in a multi-element contaminated soil profile assessed by in-situ soil pore water sampling, column leaching and sequential extraction

Three methods for predicting element mobility in soils have been applied to an iron-rich soil, contaminated with arsenic, cadmium and zinc. Soils were collected from 0 to 30 cm, 30 to 70 cm and 70 to 100 cm depths in the field and soil pore water was collected at different depths from an adjacent 100 cm deep trench. Sequential extraction and a column leaching test in the laboratory were compared to element concentrations in pore water sampled directly from the field. Arsenic showed low extractability, low leachability and occurred at low concentrations in pore water samples. Cadmium and zinc were more labile and present in higher concentrations in pore water, increasing with soil depth. Pore water sampling gave the best indication of short term element mobility when field conditions were taken into account, but further extraction and leaching procedures produced a fuller picture of element dynamics, revealing highly labile Cd deep in the soil profile.     

Arsenic accumulation and resistance mechanism in Panax notoginseng, a traditional rare medicinal herb

Panax notoginseng, a traditional rare Chinese medicinal herb, was recently found to bring health risk to consumers, mainly because soil in its major plantation area was contaminated by arsenic (As). We investigated the effect of soil As pollution on the growth and As uptake of pot-cultured P. notoginseng, and the associated mechanisms of As stressed response. Results showed that, comparing with P. notoginseng growing in a low-As soil, the root, stem, and leaf biomasses of those growing in a high-As soil significantly reduced by 0.75, 0.09 and 0.21 g seedling⁻¹, respectively. Arsenic concentrations in roots, stems and leaves of the seedlings growing in high-As soil were 22, 15 and 3 times higher than those growing in low-As soil, respectively. Regardless of the soil As concentration, As existed in plants mainly as As(III), suggesting that the reduction of As(V) is a key step in As metabolism. Arsenic was distributed primarily in cell walls (51.7% for plants growing in the low-As soil, and 51.5% in the high-As soil), followed by cytoplasm supernatant, with cell organelles containing the least As. Compared with plants growing in the low-As soil, those in the high-As soil had increased superoxide dismutase and peroxidase activities in their roots, stems, and leaves, which would be associate with improving the resistance of P. notoginseng to As stress. The results suggest that there exists some special mechanisms of As-tolerance in P. notoginseng and the study is of significance in developing measures to reduce As in the herb.     

The impact of seasonal variations in DOC arising from a moorland peat catchment on coagulation with iron and aluminium salts

Natural organic matter (NOM) is one of the main sources of environmental pollution to drinking water supplies in much of the UK and the US. Whilst traditional treatment with trivalent coagulants has proven a successful strategy in the past, operational problems are now being reported during periods of elevated organic levels in the water. Characterisation of the pollutants in terms of polarity, molecular weight and charge, provides a method to understand the impact of the observed temporal and spatial variations in terms of a mechanistic parameter relevant to the treatment processes. Results from this study demonstrate that it is not simply the increased organic concentration, but also the change in NOM composition and character, which influences the impact on the treatment processes. Consequently, monitoring of these parameters provides an insight into how to manage the impact caused by environmental changes to the catchments.     

Assessing pesticide concentrations and fluxes in the stream of a small vineyard catchment - Effect of sampling frequency

This study reports on the occurrence and behaviour of six pesticides and one metabolite in a small stream draining a vineyard catchment. Base flow and flood events were monitored in order to assess the variability of pesticide concentrations according to the season and to evaluate the role of sampling frequency on the evaluation of fluxes estimates. Results showed that dissolved pesticide concentrations displayed a strong temporal and spatial variability. A large mobilisation of pesticides was observed during floods, with total dissolved pesticide fluxes per event ranging from 5.7 × 10⁻³ g/Ha to 0.34 g/Ha. These results highlight the major role of floods in the transport of pesticides in this small stream which contributed to more than 89% of the total load of diuron during August 2007. The evaluation of pesticide loads using different sampling strategies and method calculation, showed that grab sampling largely underestimated pesticide concentrations and fluxes transiting through the stream.     

Temporal variability in dynamic and colloidal metal fractions determined by high resolution in situ measurements in a UK estuary

In recent environmental legislation, such as the Water Framework Directive in the European Union (WFD, 2000/60/EC), the importance of metal speciation and biological availability is acknowledged, although analytical challenges remain. In this study, the Voltammetric In situ Profiler (VIP) was used for high temporal resolution in situ metal speciation measurements in estuarine waters. This instrument simultaneously determines Cd, Cu and Pb species within a size range (ca. <4 nm) that is highly relevant for uptake by organisms. The colloidal metal fraction can be quantified through a combination of VIP measurements and analyses of total dissolved metal concentrations.VIP systems were deployed over tidal cycles in a seasonal study of metal speciation in the Fal Estuary, southwest England. Total dissolved concentrations were 4.97-315 nM Cu, 0.13-8.53 nM Cd and 0.35-5.75 nM Pb. High proportions of Pb (77 ± 17%) and Cu (60 ± 25%) were present as colloids, which constituted a less important fraction for Cd (37 ± 30%). The study elucidated variations in the potentially toxic metal fraction related to river flow, complexation by organic ligands and exchanges between dissolved and colloidal phases and the sediment. Based on published toxicity data, the bioavailable Cu concentrations (1.7-190 nM) in this estuary are likely to severely compromise the ecosystem structure and functioning with respect to species diversity and recruitment of juveniles. The study illustrates the importance of in situ speciation studies at high resolution in pursuit of a better understanding of metal (bio)geochemistry in dynamic coastal systems.     

Source term characterisation using concentration trends and geochemical associations of Pb and Zn in river sediments in the vicinity of a disused mine site: Implications for contaminant metal dispersion processes

River sediment at a disused lead-zinc mine was analysed to provide an understanding of the chemical nature of the source term for contaminated sediment exported from the site. Changes in concentration and geochemical associations of Pb and Zn were measured using aqua regia digestion and the BCR sequential extraction procedure. Sediment in the immediate vicinity of the mine was highly contaminated with Pb (max. c. 11,000 mg kg⁻¹) and Zn (max. c. 30,000 mg kg⁻¹), but these values declined rapidly within 1 km of the mine due to dilution and hydraulic sorting. Lead fractionation changed from being predominantly in the reducible fraction to being in the acetic acid-extractable fraction, whereas Zn was predominantly in the residual fraction. This material is transported as fine sediment in the river system.     

Laboratory migration experiments with radionuclides and natural colloids in a granite fracture

Natural colloids in groundwater could facilitate radionuclide transport, provided the colloids are mobile, are present in sufficient concentrations and can adsorb radionuclides. This paper describes the results of a laboratory migration study carried out with combinations of radionuclides and natural colloids within a fracture in a large granite block to experimentally determine the impact of colloids on radionuclide transport. The 85Sr used in this study is an example of a moderately sorbing radionuclide, while the 241Am is typical of a strongly sorbed radionuclide with very low solubility. The natural colloids used in this study were isolated from granite groundwater from Atomic Energy of Canada (AECL) Underground Research Laboratory (URL), and consisted of mostly 1-10 nm organic colloids, along with lesser amounts of 10-450 nm colloids (organics and aluminosilicates). The measured coefficients for radionuclide sorption onto these colloids were between 3 x 10(2) and 1 x 10(3) ml/g for 85Sr, and between 7 x 10(4) and 7 x 10(5) mg/l for 241Am. The 85Sr sorption on the natural colloids appeared to be reversible. Migration experiments in the granite block were carried out by establishing a flow field between two boreholes (out of a total of nine) intersecting a main horizontal fracture. These experiments showed that dissolved 85Sr behaved as a moderately sorbing tracer, while dissolved 241Am was completely adsorbed by the fracture surfaces and showed no evidence of transport. However, when natural colloids were injected together with dissolved 241Am, a small amount of 241Am transport was observed, demonstrating the ability of natural colloids to facilitate the transport of radionuclides with low solubility. Natural colloids had only a minor effect on the transport of 85Sr. In a separate experiment to test the effect of higher colloid concentrations on 85Sr migration, synthetic colloids were produced from Avonlea bentonite. The introduction of a relatively high concentration of bentonite colloids actually reduced 85Sr transport because, compared to natural colloids, the bentonite colloids were less mobile and they sorbed 85Sr more strongly.     

Alterations to proteome and tissue recovery responses in fish liver caused by a short-term combination treatment with cadmium and benzo[a]pyrene

The livers of soles (Solea senegalensis) injected with subacute doses of cadmium (Cd), benzo[a]pyrene (B[a]P), or their combination, were screened for alterations to cytosolic protein expression patterns, complemented by cytological and histological analyses. Cadmium and B[a]P, but not combined, induced hepatocyte apoptosis and Kupfer cell hyperplasia. Proteomics, however, suggested that apoptosis was triggered through distinct pathways. Cadmium and B[a]P caused upregulation of different anti-oxidative enzymes (peroxiredoxin and glutathione peroxidase, respectively) although co-exposure impaired induction. Similarly, apoptosis was inhibited by co-exposure, to which may have contributed a synergistic upregulation of tissue metalloproteinase inhibitor, β-actin and a lipid transport protein. The regulation factors of nine out of eleven identified proteins of different types revealed antagonistic or synergistic effects between Cd and B[a]P at the prospected doses after 24 h of exposure. The results indicate that co-exposure to Cd and B[a]P may enhance toxicity by impairing specific responses and not through cumulative damage.     

Cadmium concentration and distribution in corn (zea mays L.) grown on a calcareous soil for three years after three annual sludge applications

Abstract

The disposal of digested sewage sludge on crop‐producing land appeals to municipalities as an option but may pose a hazard to human and animal health if the plant material contains elevated levels of some heavy metals. This paper reports the levels of cadmium in corn grain and stover for six years — three years with sludge applied annually and for three years after sludge applications were terminated. The cadmium concentration in corn grain from the sixth year was similar to values found in corn grown on non‐sludged plots. In corn stover fron treated plots the cadmium concentration was greater than from untreated plots. Our. study indicated that phytotoxic levels of cadmium did not exist even though elevated levels occurred in the corn stover.     

Specific accumulation of cadmium and other trace elements in Sarcodon imbricatus using ICP-MS with a chemometric approach

Fungi can effectively accumulate various metallic elements, metalloids and non-metals in fruiting bodies. This study provides information on the accumulation of Ag, As, Ba, Cd, Co, Cs, Cu, Cr, Li, Mn, Ni, Pb, Rb, Sr, V, Tl, U and Zn in the edible mushroom Sarcodon imbricatus (L.) P. Karst. using the technique of inductively coupled plasma – mass spectrometry with a dynamic reaction cell mode. Mushrooms were foraged from four regions in Poland. Baseline concentrations of minerals, expressed in mg kg^?1 dry biomass (db), were in the composite samples of caps in the range: for Ag (0.27–0.29), As (1.0–1.9), Ba (0.31–0.45), Cd (4.5–6.3), Co (0.23–1.9), Cu (28–35), Cr (0.19–0.29), Cs (20–38), Li (0.013–0.020), Mn (5.9–8.8), Ni (0.81–1.4), Pb (0.94–1.6), Rb (490–700), Sr (0.14–0.19), Tl (0.058–0.11), U (0.002–0.002), V (0.044–0.054) and Zn (140–160). Concentration levels of Ag, As, Cd, Cs, Pb and Zn were higher in caps than in stipes of S. imbricatus, whereas for other elements the distribution between caps and stipes was nearly equal or for some differed depending on the location. Certainly, the content of toxic Cd in S. imbricatus was elevated (0.45–0.63 mg kg^?1 in fresh caps) and therefore eating this mushroom could increase exposure to Cd. In addition, the content of toxic As in S. imbricatus was elevated.     

Reduction of dioxin emission by a multi-layer reactor with bead-shaped activated carbon in simulated gas stream and real flue gas of a sinter plant

A laboratory-scale multi-layer system was developed for the adsorption of PCDD/Fs from gas streams at various operating conditions, including gas flow rate, operating temperature and water vapor content. Excellent PCDD/F removal efficiency (>99.99%) was achieved with the multi-layer design with bead-shaped activated carbons (BACs). The PCDD/F removal efficiency achieved with the first layer adsorption bed decreased as the gas flow rate was increased due to the decrease of the gas retention time. The PCDD/F concentrations measured at the outlet of the third layer adsorption bed were all lower than 0.1 ng I-TEQ Nm⁻³. The PCDD/Fs desorbed from BAC were mainly lowly chlorinated congeners and the PCDD/F outlet concentrations increased as the operating temperature was increased. In addition, the results of pilot-scale experiment (real flue gases of an iron ore sintering plant) indicated that as the gas flow rate was controlled at 15 slpm, the removal efficiencies of PCDD/F congeners achieved with the multi-layer reactor with BAC were better than that in higher gas flow rate condition (20 slpm). Overall, the lab-scale and pilot-scale experiments indicated that PCDD/F removal achieved by multi-layer reactor with BAC strongly depended on the flow rate of the gas stream to be treated.     

Mobility of Cd and Cu in formulated sediments coated with iron hydroxides and/or humic acids: a DGT and DGT-PROFS modeling approach

The diffusive gradients technique in thin films (DGT) was used to investigate the kinetic resupply of Cd and Cu to pore water from the solid phase. For the sake of simplification, experiments were performed using formulated sediments that differed in the presence or absence of humic acids (HA) and/or of iron hydroxides (i.e., goethite and ferrihydrite). The effects of the time after the contamination of the solid phase (aging effect) on formulated sediments that were coated with goethite and HA and spiked with Cd were also evaluated. Kinetic DGT results were interpreted using the newly developed, multi-compartmental model DGT-PROFS.Due to Cu humate formation, the addition of HA slightly increased the Cu concentration in the pore water independent of the effect of the iron hydroxide coating on the formulated sediments and slightly decreased that of Cd. The impact of 8-190 d of aging resulted in a significant decrease in the Cd concentration of the pore water over an increasing incubation time.Modeling our results with DGT-PROFS led to the following conclusions concerning the impact of HA and iron hydroxides on Cd and Cu availability. First, in the presence of HA and absence of iron hydroxides, Cd is associated mainly with weak sites, while Cu is bound to strong sites. Similarly, in the presence of both iron hydroxides and HA, Cu appeared to be more heavily associated with the strong sites than did Cd. When the incubation time increased from 8 to 190 d, a proportion of Cd initially adsorbed onto weak sites transferred to the strong sites, suggesting that the adsorption of Cd on sediments is controlled partially by slow kinetic processes.     

Powdered activated carbon coupled with enhanced coagulation for natural organic matter removal and disinfection by-product control: application in a Western Australian water treatment plant

The removal of organic precursors of disinfection by-products (DBPs), i.e. natural organic matter (NOM), prior to disinfection and distribution is considered as the most effective approach to minimise the formation of DBPs. This study investigated the impact of the addition of powdered activated carbon (PAC) to an enhanced coagulation treatment process at an existing water treatment plant on the efficiency of NOM removal, the disinfection behaviour of the treated water, and the water quality in the distribution system. This is the first comprehensive assessment of the efficacy of plant-scale application of PAC combined with enhanced coagulation on an Australian source water. As a result of the PAC addition, the removal of NOM improved by 70%, which led to a significant reduction (80-95%) in the formation of DBPs. The water quality in the distribution system also improved, indicated by lower concentrations of DBPs in the distribution system and better maintenance of disinfectant residual at the extremities of the distribution system. The efficacy of the PAC treatment for NOM removal was shown to be a function of the characteristics of the NOM and the quality of the source water, as well as the PAC dose. PAC treatment did not have the capacity to remove bromide ion, resulting in the formation of more brominated DBPs. Since brominated DBPs have been found to be more toxic than their chlorinated analogues, their preferential formation upon PAC addition must be considered, especially in source waters containing high concentrations of bromide.     

Treatment of dynamic mixture of hexane and benzene vapors in a Trickle Bed Air Biofilter integrated with cyclic adsorption/desorption beds

One of the main challenges that face successful biofiltration is the erratic loading pattern and long starvation periods. However, such patterns are common in practical applications. In order to provide long-term stable operation of a biofilter under these conditions, a cyclic adsorption/desorption beds system with flow switching was installed prior to a biofilter. Different square waves of a mixture containing n-hexane and benzene at a 2:1 ratio were applied to the cyclic adsorption/desorption beds and then fed to a biofilter. The performance of this integrated system was compared to a biofilter unit receiving the same feed of both VOCs. The cyclic adsorption/desorption beds unit successfully achieved its goal of stabilizing erratic loading even with very sharp peaks at the influent concentration equalizing influent concentrations ranging from 10-470 ppmv for n-hexane to 30-1410 ppmv for benzene. The study included different peak concentrations with durations ranging from 6 to 20 min. The cyclic beds buffered the fluctuating influent load and the followed biofilter had all the time a continuous stable flow. Another advantage achieved by the cyclic adsorption/desorption beds was the uninterrupted feed to the biofilter even during the starvation where there was no influent in the feed. The results of the integrated system with regard to removal efficiency and kinetics are comparable to published results with continuous feed studies at the same loading rates. The removal efficiency for benzene had a minimum of 85% while for n-hexane ranged from 50% to 77% according to the loading rate. The control unit showed very erratic performance highlighting the benefit of the utilization of the cyclic adsorption/desorption beds. The biofilter was more adaptable to concentration changes in benzene than n-hexane.