Recycling of EDTA solution after soil washing of Pb, Zn, Cd and As contaminated soil

Soil washing with EDTA is known to be an effective means of removing toxic metals from contaminated soil. A practical way of recycling of used soil washing solution remains, however, an unsolved technical problem. We demonstrate here, in a laboratory scale experiment, the feasibility of using acid precipitation to recover up to 50% of EDTA from used soil washing solution obtained after extraction of Pb (5330 mg kg⁻¹), Zn (3400 mg kg⁻¹), Cd (35 mg kg⁻¹) and As (279 mg kg⁻¹) contaminated soil. Up to 100% of EDTA residual in the washing solution and 100%, 97%, 98% and 100% of initial Pb, Zn, Cd and As concentration in the solution, respectively, were removed in an electrolytic cell using a graphite anode. We employed the recovered EDTA and treated washing solution to prepare recycled soil washing solution with the same potential for extracting toxic metals from soil as the original. The efficiency of soil washing depends on the EDTA concentration. Using twice recycled 30 mmol EDTA kg⁻¹ soil, we removed 44%, 20%, 53% and 61% of Pb, Zn, Cd and As, respectively, from contaminated soil.     

Impact of earthworms on trace element solubility in contaminated mine soils amended with green waste compost

The common practice of remediating metal contaminated mine soils with compost can reduce metal mobility and promote revegetation, but the effect of introduced or colonising earthworms on metal solubility is largely unknown. We amended soils from an As/Cu (1150 mgAs kg⁻¹ and 362 mgCu kg⁻¹) and Pb/Zn mine (4550 mgPb kg⁻¹ and 908 mgZn kg⁻¹) with 0, 5, 10, 15 and 20% compost and then introduced Lumbricus terrestris. Porewater was sampled and soil extracted with water to determine trace element solubility, pH and soluble organic carbon. Compost reduced Cu, Pb and Zn, but increased As solubility. Earthworms decreased water soluble Cu and As but increased Pb and Zn in porewater. The effect of the earthworms decreased with increasing compost amendment. The impact of the compost and the earthworms on metal solubility is explained by their effect on pH and soluble organic carbon and the environmental chemistry of each element.     

Chelant-aided enhancement of lead mobilization in residential soils

Chelation of metals is an important factor in enhancing solubility and hence, availability to plants to promote phytoremediation. We compared the effects of two chelants, namely, ethylenediaminetetraacetic acid (EDTA) and ethylenediaminedisuccinic acid (EDDS) in enhancing mobilized lead (Pb) in Pb-based paint contaminated residential soils collected from San Antonio, Texas and Baltimore, Maryland. Batch incubation studies were performed to investigate the effectiveness of the two chelants in enhancing mobilized Pb, at various concentrations and treatment durations. Over a period of 1 month, the mobilized Pb pool in the San Antonio study soils increased from 52 mg kg⁻¹ to 287 and 114 mg kg⁻¹ in the presence of 15 mM kg⁻¹ EDTA and EDDS, respectively. Stepwise linear regression analysis demonstrated that pH and organic matter content significantly affected the mobilized Pb fraction. The regression models explained a large percentage, from 83 to 99%, of the total variation in mobilized Pb concentrations.     

Estimation of daily intake of potentially toxic elements from urban street dust and the role of oral bioaccessibility testing

The pseudo-total and oral bioaccessible concentration of six potentially toxic elements (PTEs) in urban street dust was investigated. Typical pseudo-total concentrations across the sampling sites ranged from 4.4 to 8.6 mg kg⁻¹ for As, 0.2-3.6 mg kg⁻¹ for Cd, 25-217 mg kg⁻¹ for Cu, 14-46 mg kg⁻¹ for Ni, 70-4261 mg kg⁻¹ for Pb, and, 111-652 mg kg⁻¹ for Zn. This data compared favourably with other urban street dust samples collected and analysed in a variety of cities globally; the exception was the high level of Pb determined in a specific sample in this study. The oral bioaccessibility of PTEs in street dust is also assessed using in vitro gastrointestinal extraction (Unified Bioaccessibility Method, UBM). Based on a worst case scenario the oral bioaccessibility data estimated that Cd and Zn had the highest % bioaccessible fractions (median >45%) while the other PTEs i.e. As, Cu, Ni and Pb had lower % bioaccessible fractions (median <35%). The pseudo-total and bioaccessible concentrations of PTEs in the samples has been compared to estimated tolerable daily intake values based on unintentional soil/dust consumption. Cadmium, Cu and Ni are well within the oral tolerable daily intake rates. With respect to As and Pb, only the latter exceeds the TDI_oral if we model ingestion rate based on atmospheric ‘dustiness’ rather than the US EPA (2008) unintentional soil/dust consumption rate of 100 mg d⁻¹. We consider it unlikely that even a child with pica tendencies would ingest as much as 100 mg soil/dust during a daily visit to the city centre, and in particular to the sites with elevated Pb concentrations observed in this study.     

Lead contamination of the Seine River, France: geochemical implications of a historical perspective

Four sediment cores collected in the Seine River basin and dated between 1916 and 2003 were analyzed for lead concentrations and isotopic composition. In all four cores, the measured Pb concentration (up to 460 mg kg⁻¹) lies significantly above the natural background (27-40 mg kg⁻¹), although a significant decrease (down to 75 mg kg⁻¹) was observed during the second half of the 20th century which can be explained by the reduction of lead emissions. The ²⁰⁶Pb/²⁰⁷Pb ratio measured in these samples indicates that the main source of Pb used in the Paris conurbation is characterized by a “Rio Tinto” signature (defined as ²⁰⁶Pb/²⁰⁷Pb = 1.1634 ± 0.0001). A high contribution, up to 25%, from the leaded gasoline (characterized by ²⁰⁶Pb/²⁰⁷Pb = 1.08 ± 0.02) is revealed in the Seine River downstream Paris, indicating that lead from the leaded gasoline is preferentially released to the river.The dominating Pb signature in the Paris conurbation that is currently sampled through incinerators fumes (²⁰⁶Pb/²⁰⁷Pb = 1.1550 ± 0.0005) and waste water treatment plant (²⁰⁶Pb/²⁰⁷Pb = 1.154 ± 0.002), represents a mixture of highly recycled lead from the Rio Tinto mine and lead from leaded gasoline (imprinted by the low ²⁰⁶Pb/²⁰⁷Pb of the Broken Hill mine). This signature is called “urban” rather than “industrial”, because it is clearly distinct from the Pb that is found in areas contaminated by heavy industry, i.e. the heavy industries located on the Oise River which used lead from European ores characterized by high ²⁰⁶Pb/²⁰⁷Pb ratios (∼1.18-1.19) and possibly a minor amount of North American lead (²⁰⁶Pb/²⁰⁷Pb ratios > 1.20). The “urban” signature is also found in a rural area upstream of Paris in the 1970’s. At the Seine River mouth in 2003, Pb with an urban signature represents 70% of the total Pb sediment content, with the 30% remaining corresponding to natural Pb.     

Effects of biochar and the earthworm Eisenia fetida on the bioavailability of polycyclic aromatic hydrocarbons and potentially toxic elements

Polycyclic aromatic hydrocarbons (PAHs) and potentially toxic elements (PTEs) were monitored over 56 days in calcareous contaminated-soil amended with either or both biochar and Eisenia fetida. Biochar reduced total (449 to 306 mg kg⁻¹) and bioavailable (cyclodextrin extractable) (276 to 182 mg kg⁻¹) PAHs, PAH concentrations in E. fetida (up to 45%) but also earthworm weight. Earthworms increased PAH bioavailability by >40%. Combined treatment results were similar to the biochar-only treatment. Earthworms increased water soluble Co (3.4 to 29.2 mg kg⁻¹), Cu (60.0 to 120.1 mg kg⁻¹) and Ni (31.7 to 83.0 mg kg⁻¹) but not As, Cd, Pb or Zn; biochar reduced water soluble Cu (60 to 37 mg kg⁻¹). Combined treatment results were similar to the biochar-only treatment but gave a greater reduction in As and Cd mobility. Biochar has contaminated land remediation potential, but its long-term impact on contaminants and soil biota needs to be assessed.     

Correlation of foliar MT2b expression with Cd and Zn concentrations in hybrid aspen (Populus tremula × tremuloides) grown in contaminated soil

Metal uptake and its effect on foliar metallothionein 2b (MT2b) mRNA levels were studied in hybrid aspen (Populus tremula × tremuloides) in field conditions. The trees were planted on a site contaminated with several metals, including cadmium (mean 5.1 mg kg⁻¹), chromium (80 mg kg⁻¹), copper (180 mg kg⁻¹), nickel (81 mg kg⁻¹), vanadium (240 mg kg⁻¹) and zinc (520 mg kg⁻¹). Of the ten trace elements analyzed, only Cd and Zn accumulated in the leaves with maximal foliar concentrations of 35 and 2400 mg kg⁻¹ (dry weight), respectively. There was a strong correlation between Cd and Zn concentrations and bioaccumulation factors (concentration in plant/soil) in the leaves, branches and roots, suggesting similar transport mechanisms for these two metals. The levels of MT2b correlated with Cd and Zn concentrations in the leaves, demonstrating that increased MT2b expression is one of the responses of hybrid aspen to chronic metal exposure.     

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.     

Toxicity and metabolism of copper pyrithione and its degradation product, 2,2'-dipyridyldisulfide in a marine polychaete

We conducted acute toxicity tests and sediment toxicity tests for copper pyrithione (CuPT) and a metal pyrithione degradation product, 2,2′-dipyridyldisulfide [(PS)₂], using a marine polychaete Perinereis nuntia. The acute toxicity tests yielded 14-d LC₅₀ concentrations for CuPT and (PS)₂ of 0.06 mg L⁻¹ and 7.9 mg L⁻¹, respectively. Sediment toxicity tests resulted in 14-d LC₅₀ concentrations for CuPT and (PS)₂ of 1.1 mg kg⁻¹ dry wt. and 14 mg kg⁻¹ dry wt., respectively. In addition to mortality, sediment avoidance behavior and decreases in animal growth rate were observed; growth rate was the most susceptible endpoint in the sediment toxicity tests of both toxicants. Thus, we propose lowest observed effect concentrations of 0.3 mg kg⁻¹ dry wt. and 0.2 mg kg⁻¹ dry wt. for CuPT and (PS)₂, respectively, and no observed effect concentrations of 0.1 mg kg⁻¹ dry wt. for both CuPT and (PS)₂. The difference in the toxicity values between CuPT and (PS)₂ observed in the acute toxicity test was greater than the difference in these values in the sediment toxicity test, and we attribute this to (PS)₂ being more hydrophilic than CuPT. In addition to the toxicity tests, we analyzed conjugation activity of several polychaete enzymes to the toxicants and marked activity of palmitoyl coenzyme-A:biocides acyltransferase and UDP-glucuronosyl transferase was observed.     

Influence of electrical fields (AC and DC) on phytoremediation of metal polluted soils with rapeseed (Brassica napus) and tobacco (Nicotiana tabacum)

The combined use of electrokinetic remediation and phytoremediation to decontaminate soil polluted with heavy metals has been demonstrated in a laboratory-scale experiment. The plants species selected were rapeseed and tobacco. Three kinds of soil were used: un-contaminated soil from forest area (S1), artificially contaminated soil with 15 mg kg⁻¹ Cd (S2) and multi-contaminated soil with Cd, Zn and Pb from an industrial area (S3). Three treatment conditions were applied to the plants growing in the experimental vessels: control (no electrical field), alternating current electrical field (AC, 1 V cm⁻¹) and direct current electrical field (DC, 1 V cm⁻¹) with switching polarity every 3 h. The electrical fields were applied for 30 d for rapeseed and 90 d for tobacco, each experiment had three replicates. After a total of 90 d growth for rapeseed and of 180 d for tobacco, the plants were harvested. The pH variation from anode to cathode was eliminated by switching the polarity of the DC field. The plants reacted differently under the applied electrical field. Rapeseed biomass was enhanced under the AC field and no negative effect was found under DC field. However, no enhancement of the tobacco biomass under the AC treatment was found. The DC field had a negative influence on biomass production on tobacco plants. In general, Cd content was higher in both species growing in S2 treated with AC field compared to the control. Metal uptake (Cd, Cu, Zn and Pb) per rapeseed plant shoot was enhanced by the application of AC field in all soils.     

Arsenic speciation in field-collected and laboratory-exposed earthworms Lumbricus terrestris

Mature Lumbricus terrestris were host soils and leaf litter were collected from a former arsenic mine in Devon, UK (Devon Great Consols), a former gold mine in Ontario, Canada (Deloro), and an uncontaminated residential garden in Nottingham, UK. Arsenic concentrations determined by inductively coupled plasma-mass spectrometry (ICP-MS) in soils were 16-348 mg kg⁻¹, 6.0-239 mg kg⁻¹ in the earthworms and 8.6 mg kg⁻¹ in leaf litter sampled at Deloro (all dry weight). High performance liquid chromatography (HPLC-ICP-MS) analysis revealed arsenite (As^III), arsenate (As^V) and five organoarsenic species; arsenobetaine (AB), methylarsonate (MA^V), dimethylarsinate (DMA^V), arsenosugar 1 (glycerol sugar), arsenosugar 2 (phosphate sugar), and trimethylarsineoxide (TMAO) in field-collected L. terrestris. Differences were observed in the variety of organoarsenic species present between field sites. Several organoarsenic species were observed in the leaf litter (DMA^V, arsenosugar 2 and TMAO) but not AB. Depuration resulted in higher concentrations of inorganic As being detected in the earthworm whereas the concentration or variety of organoarsenic species was unchanged. Commercially sourced L. terrestris were exposed to As contaminated soil in laboratory mesocosms (1.0, 98, 183, 236, 324 and 436 mg kg⁻¹) without leaf litter and were additionally analyzed using X-ray absorption near edge structure (XANES). Only inorganic As^III and As^V was observed. It is proposed that ingestion of leaf litter and symbiotic processes in the natural soil environment are likely sources of organoarsenic compounds in field-collected L. terrestris.     

Amendment of arsenic and chromium polluted soil from wood preservation by iron residues from water treatment

An iron-rich water treatment residue (WTR) consisting mainly of ferrihydrite was used for immobilization of arsenic and chromium in a soil contaminated by wood preservatives. A leaching batch experiment was conducted using two soils, a highly contaminated soil (1033 mg kg⁻¹ As and 371 mg kg⁻¹ Cr) and slightly contaminated soil (225 mg kg⁻¹ As and 27 mg kg⁻¹ Cr). Compared to an untreated reference soil, amendment with 5% WTR reduced leaching in the highly contaminated soil by 91% for Cr and 98% for As. No aging effect was observed after 103 d. In a small field experiment, soil was mixed with 2.5% WTR in situ. Pore water was extracted during 3 years from the amended soil and a control site. Pore water arsenic concentrations in the amended soil were more than two orders of magnitude lower than in the control for the upper samplers. An increased release of arsenic was observed during winter in both fields, mostly in the deepest samplers. This is likely due to the formation of a pseudo-gley because of precipitation surplus. Stabilization of arsenic and chromium contaminated soil using WTR is a promising method but the transformation of ferrihydrite in soil proves a concern in case of waterlogged soils. Still the amendment minimized the leaching of arsenic, even in cases of seasonal releases.     

Long-term records of cadmium and silver contamination in sediments and oysters from the Gironde fluvial-estuarine continuum - evidence of changing silver sources

The Gironde fluvial estuarine system is impacted by historic metal pollution (e.g. Cd, Zn, Hg) and oysters (Crassostrea gigas) from the estuary mouth have shown extremely high Cd concentrations for decades. Based on recent work (Chiffoleau et al., 2005) revealing anomalously high Ag concentrations (up to 65 mg kg⁻¹; dry weight) in Gironde oysters, we compared long-term (∼1955-2001) records of Ag and Cd concentrations in reservoir sediment with the respective concentrations in oysters collected between 1979 and 2010 to identify the origin and historical trend of the recently discovered Ag anomaly. Sediment cores from two reservoirs upstream and downstream from the main metal pollution source provided information on (i) geochemical background (upstream; Ag: ∼0.3 mg kg⁻¹; Cd: ∼0.8 mg kg⁻¹) and (ii) historical trends in Ag and Cd pollution. The results showed parallel concentration-depth profiles of Ag and Cd supporting a common source and transport. Decreasing concentrations since 1986 (Cd: from 300 to 11 mg kg⁻¹; Ag: from 6.7 to 0.43 mg kg⁻¹) reflected the termination of Zn ore treatment in the Decazeville basin followed by remediation actions. Accordingly, Cd concentrations in oysters decreased after 1988 (from 109 to 26 mg kg⁻¹, dry weight (dw)), while Ag bioaccumulation increased from 38 up to 116 mg kg⁻¹, dw after 1993. Based on the Cd/Ag ratio (Cd/Ag ∼ 2) in oysters sampled before the termination of zinc ore treatment (1981-1985) and assuming that nearly all Cd in oysters originated from the metal point source, we estimated the respective contribution of Ag from this source to Ag concentrations in oysters. The evolution over the past 30 years clearly suggested that the recent, unexplained Ag concentrations in oysters are due to increasing contributions (>70% after 1999) by other sources, such as photography, electronics and emerging Ag applications/materials.     

Feasibility of phytoextraction to remediate cadmium and zinc contaminated soils

A Cd and Zn contaminated soil was mixed and equilibrated with an uncontaminated, but otherwise similar soil to establish a gradient in soil contamination levels. Growth of Thlaspi caerulescens (Ganges ecotype) significantly decreased the metal concentrations in soil solution. Plant uptake of Cd and Zn exceeded the decrease of the soluble metal concentrations by several orders of magnitude. Hence, desorption of metals must have occurred to maintain the soil solution concentrations. A coupled regression model was developed to describe the transfer of metals from soil to solution and plant shoots. This model was applied to estimate the phytoextraction duration required to decrease the soil Cd concentration from 10 to 0.5 mg kg⁻¹. A biomass production of 1 and 5 t dm ha⁻¹ yr⁻¹ yields a duration of 42 and 11 yr, respectively. Successful phytoextraction operations based on T. caerulescens require an increased biomass production.     

Sources of PCDD/Fs, non-ortho PCBs and PAHs in sediments of high and low impacted transboundary rivers (Belgium-France)

PAHs, PCDD/Fs and non-ortho PCBs have been assessed in Yser and Upper-Scheldt river sediments. Higher contamination levels were observed in the Upper-Scheldt sediments: maximum concentrations for the 16 US-EPA PAHs, PCDD/Fs and non-ortho PCBs respectively amount to 8.9 mg kg⁻¹, 12 ng TEQ kg⁻¹ and 5.1 ng TEQ kg⁻¹. Diagnostic PAH ratios in sediments and atmospheric samples suggest that the PAH compounds are from pyrolytic origin, more specifically combustion processes. The huge consumption of coal in cokes-ovens and smelters and its use for house-heating in Northern France, although decreasing during the last decades, are in support of that suggestion. PCDD/F fingerprints in sediments and deposition material indicate that OCDD is the dominant congener. In addition use of pentachlorophenol (PCP) in the past led to a minor contribution of PCDD/Fs in our sediment samples. Non-ortho PCBs form a substantial fraction of the total TEQ concentrations observed in the sediments. Since the 1980s and 1990s a substantial reduction of the PCDD/F sediment concentrations is observed, but this is not the case for the PAHs.     

Hyperaccumulation of zinc by Corydalis davidii in Zn-polluted soils

A field survey was conducted to identify potential Zn accumulators from an artisanal Zn smelting area in southwest China’s Guizhou Province. Hydroponic and soil culture experiments were performed to investigate the accumulation ability of Zn in Corydalis davidii. Zn concentrations in roots, stems and leaves of C. davidii in the smelting site were 1.1-3.5, 1.2-11.2, and 3.3-14 mg g⁻¹, respectively, whereas Zn concentrations in roots, stems and leaves of C. davidii in the contaminated site impacted by the Zn smelting were 1.0-2.4, 1.9-6.5, and 3.0-1.1 mg g⁻¹, respectively. Zn concentrations in leaves and stems of C. davidii were observed at above 10 mg g⁻¹ that refers to the threshold of Zn hyperaccumulator. The concentration distribution of Zn in C. davidii was leaf > stem > root, and the Zn bioaccumulation factors of C. davidii were above 1. It is concluded that C. davidii has high tolerance to concentrate Zn stress, and that C. davidii is a newly discovered Zn-hyperaccumulator with high biomass in the aboveground parts. Based on the cultivation experiments, C. davidii could reduce Zn concentration by 26.6, 21.2, and 10.2 mg kg⁻¹yr⁻¹ by phytoextraction from the smelting slag, Zn-contaminated soil, and background soil, respectively.     

Influences of sediment dessication on phosphorus transformations in an intertidal marsh: formation and release of phosphine

This study investigated the effects of sediment dewatering on the phosphorus transformations concerning about the production and emission of phosphine in the intertidal marsh of the Yangtze Estuary. The concentrations of matrix-bound phosphine ranged from 18.62-72.53 ng kg⁻¹ and 31.14-61.22 ng kg⁻¹ within the August and January exposure incubations, respectively. The responses of matrix-bound phosphine concentrations to sediment dessication demonstrate that the production (or accumulation) of matrix-bound phosphine significantly increased with water loss at the start of the emersion incubations. However, further dehydration inhibited the formation of matrix-bound phosphine in sediments. The significant correlations of matrix-bound phosphine with the organic-P bacteria abundance and alkaline phosphatase activities implicate that the production of matrix-bound phosphine within the dessication incubations was linked closely to the microbial decomposition of organic P. The emissions of phosphine generally decreased with sediment dewatering, with the fluxes of 7.51-96.73 ng m⁻² h⁻¹ and 5.34-77.74 ng m⁻² h⁻¹ over the exposure incubations of both August and January, respectively. Also, it is observed that the releases of phosphine during the entire exposure periods were affected not only by its production but also by sediment water and redox conditions.     

Root porosity and radial oxygen loss related to arsenic tolerance and uptake in wetland plants

The rates of radial oxygen loss (ROL), root porosity, concentrations of arsenic (As), iron (Fe) and manganese (Mn) in shoot and root tissues and on root surfaces, As tolerances, and their relationships in different wetland plants were investigated based on a hydroponic experiment (control, 0.8, 1.6 mg As L⁻¹) and a soil pot trail (control, 60 mg As kg⁻¹). The results revealed that wetland plants showed great differences in root porosity (9-64%), rates of ROL (55-1750 mmo1 O₂ kg⁻¹ root d.w. d⁻¹), As uptake (e.g., 8.8-151 mg kg⁻¹ in shoots in 0.8 mg As L⁻¹ treatment), translocation factor (2.1-47% in 0.8 mg As L⁻¹) and tolerance (29-106% in 0.8 mg As L⁻¹). Wetland plants with higher rates of ROL and root porosity tended to form more Fe/Mn plaque, possess higher As tolerance, higher concentrations of As on root surfaces and a lower As translocation factor so decreasing As toxicity.     

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

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

Production and sedimentation of peptide toxins nodularin-R and microcystin-LR in the northern Baltic Sea

This seven-year survey was primarily targeted to quantification of production of nodularin-R (NOD-R), a cyclic pentapeptide hepatotoxin, in Baltic Sea cyanobacteria waterblooms. Additionally, NOD-R and microcystin-LR (MC-LR; a cyclic heptapeptide toxin) sedimentation rates and NOD-R sediment storage were estimated. NOD-R production (70-2450 μg m⁻³; ∼1 kg km⁻² per season) and sedimentation rates (particles; 0.03-5.7 μg m⁻² d⁻¹; ∼0.3 kg km⁻² per season) were highly variable over space and time. Cell numbers of Nodularia spumigena did not correlate with NOD-R quantities. Dissolved NOD-R comprised 57-100% of total NOD-R in the predominantly senescent, low-intensity phytoplankton blooms and seston. Unprecedentedly intensive MC-LR sedimentation (0.56 μg m⁻² d⁻¹) occurred in 2004. Hepatotoxin sedimentation rates highly exceeded those of anthropogenic xenobiotics. NOD-R storage in surficial sediments was 0.4-20 μg kg⁻¹ (∼0.1 kg km⁻²). Loss of NOD-R within the chain consisting of phytoplankton, seston and soft sediments seemed very effective.