Biochemical parameters and bacterial species richness in soils contaminated by sludge-borne metals and remediated with inorganic soil amendments

The effectiveness of two amendments for the in situ remediation of a Cd- and Ni-contaminated soil in the Louis Fargue long-term field experiment was assessed. In April 1995, one replicate plot (S1) was amended with 5% w/w of beringite (B), a coal fly ash (treatment S1+B), and a second plot with 1% w/w zerovalent-Fe iron grit (SS) (treatment S1+SS), with the aim of increasing metal sorption and attenuating metal impacts. Long-term responses of daily respiration rates, microbial biomass, bacterial species richness and the activities of key soil enzymes (acid and alkaline phosphatase, arylsulfatase, beta-glucosidase, urease and protease activities) were studied in relation to soil metal extractability. Seven years after initial amendments, the labile fractions of Cd and Ni in both the S1+B and S1+SS soils were reduced to various extents depending on the metal and fractions considered. The soil microbial biomass and respiration rate were not affected by metal contamination and amendments in the S1+B and S1+SS soils, whereas the activity of different soil enzymes was restored. The SS treatment was more effective in reducing labile pools of Cd and Ni and led to a greater recovery of soil enzyme activities than the B treatment. Bacterial species richness in the S1 soil did not alter with either treatment. It was concluded that monitoring of the composition and activity of the soil microbial community is important in evaluating the effectiveness of soil remediation practices.     

Evaluation of metal mobility, plant availability and immobilization by chemical agents in a limed-silty soil

Metal-contaminated soils in the vicinity of industrial sites become of ever-increasing concern. Diagnostic criteria and ecological technologies for soil remediation should be calibrated for various soil conditions; actually, our knowledge of calcareous soil is poor. Silty soils near smelters at Evin (Pas de Calais, France) have been contaminated by non-ferrous metal fallout and regularly limed using foams. Therefore, the mobility, bioavailability, and potential phytotoxicity of Cd, Pb and Zn, were investigated using single soil extractions (i.e. water, 0.1 n Ca(NO(3))(2), and EDTA pH 7), and vegetation experiments, in parallel with a biological test based on (iso)-enzymes in leaves and roots, before and following soil treatment with chemical agents, i.e. Thomas basic slags (TBS), hydrous manganese oxide (HMO), steel shots (ST) and beringite. No visible toxicity symptoms developed on the above-ground parts of ryegrass, tobacco and bean plants grown in potted soil under controlled environmental conditions. Cd, Zn and Pb uptake resulted in high concentrations in the above-ground plant parts, but the enzyme capacities in leaves and roots, and the peroxidase pattern indicated that these metal concentrations were not phytotoxic for beans as test plants. The addition of chemical agents to the soil did not increase biomass production, but treatment with either HMO, ST or beringite markedly decreased the mobility of Cd, Zn and Pb. These agents were proven to be effective in mitigating the Cd uptake by plants. HMO and ST decreased either Pb or Zn uptake by ryegrass. TBS was effective in lowering Pb uptake by the same species. Beringite decreased Cd uptake by beans. If fallout could be restricted, the metal content of food crops in this area should be lowered by soil treatment. However, the differences in Cd uptake between plant species were not suppressed, regardless of the type of agents applied to the soil.     

Arsenic transfer and impacts on snails exposed to stabilized and untreated As-contaminated soils

An As-contaminated soil (Unt) was amended with either iron grit (Z), a coal fly ash (beringite, B) or B + Z (BZ) and placed in lysimeters in 1997. An uncontaminated soil (R) was also studied. In summer and autumn 2003, lettuces were cultivated in the lysimeters and snails were caged for one month. Lettuce As concentrations were higher during the summer, while no differences occurred in snails between seasons. Snail As concentrations (μg g⁻¹ DW) ranged from 2.5 to 7.0 in B, Z and BZ, and peaked at 17.5 in Unt. In summer, snail survival was affected in Unt and Z compared to R and B while no mortality was noticed in autumn. Snail growth decreased only in B, BZ and Unt in autumn. Snail As concentrations suggest a risk for their predators even on the remediated soils.     

Chemical methods and phytoremediation of soil contaminated with heavy metals

The effects of chemical amendments (calcium carbonate (CC), steel sludge (SS) and furnace slag (FS)) on the growth and uptake of cadmium (Cd) by wetland rice, Chinese cabbage and wheat grown in a red soil contaminated with Cd were investigated using a pot experiment. The phytoremediation of heavy metal contaminated soil with vetiver grass was also studied in a field plot experiment. Results showed that treatments with CC, SS and FS decreased Cd uptake by wetland rice, Chinese cabbage and wheat by 23-95% compared with the unamended control. Among the three amendments, FS was the most efficient at suppressing Cd uptake by the plants, probably due to its higher content of available silicon (Si). The concentrations of zinc (Zn), lead (Pb) and Cd in the shoots of vetiver grass were 42-67%, 500-1200% and 120-260% higher in contaminated plots than in control, respectively. Cadmium accumulation by vetiver shoots was 218 g Cd/ha at a soil Cd concentration of 0.33 mg Cd/kg. It is suggested that heavy metal-contaminated soil could be remediated with a combination of chemical treatments and plants.     

Effects of alkaline and bioorganic amendments on cadmium,lead, zinc,and nutrient accumulation in brown rice and grain yield in acidic paddy fields contaminated with a mixture of heavy metals

Paddy soils and rice (Oryza sativa L.) contaminated by mixed heavy metals have given rise to great concern. Field experiments were conducted over two cultivation seasons to study the effects of steel slag (SS), fly ash (FA), limestone (LS), bioorganic fertilizer (BF), and the combination of SS and BF (SSBF) on rice grain yield, Cd, Pb, and Zn and nutrient accumulation in brown rice, bioavailability of Cd, Pb, and Zn in soil as well as soil properties (pH and catalase), at two acidic paddy fields contaminated with mixed heavy metals (Cd, Pb, and Zn). Compared to the controls, SS, LS, and SSBF at both low and high additions significantly elevated soil pH over both cultivation seasons. The high treatments of SS and SSBF markedly increased grain yields, the accumulation of P and Ca in brown rice and soil catalase activities in the first cultivation season. The most striking result was from SS application (4.0 t ha^?1) that consistently and significantly reduced the soil bioavailability of Cd, Pb, and Zn by 38.5–91.2 % and the concentrations of Cd and Pb in brown rice by 20.9–50.9 % in the two soils over both cultivation seasons. LS addition (4.0 t ha^?1) also markedly reduced the bioavailable Cd, Pb, and Zn in soil and the Cd concentrations in brown rice. BF remobilized soil Cd and Pb leading to more accumulation of these metals in brown rice. The results showed that steel slag was most effective in the remediation of acidic paddy soils contaminated with mixed heavy metals.     

The effects of biochars from rice residue on the formation of iron plaque and the accumulation of Cd, Zn, Pb, As in rice (Oryza sativa L.) seedlings

A historically multi-metal contaminated soil was amended with biochars produced from different parts of rice plants (straw, husk and bran) to investigate how biochar can influence the mobility of Cd, Zn, Pb and As in rice seedlings (Oryza sativa L.). Rice shoot concentrations of Cd, Zn and Pb decreased by up to 98%, 83% and 72%, respectively, due to biochar amendment, though that of As increased by up to 327%. Biochar amendments significantly decreased pore water concentrations (C_pw) of Cd and Zn and increased that of As. For Pb it depended on the amendment. Porewater pH, dissolved organic carbon, dissolved phosphorus, silicon in pore water and iron plaque formation on root surfaces all increased significantly after the amendments. The proportions of Cd and Pb in iron plaque increased by factors 1.8-5.7 and 1.4-2.8, respectively; no increase was observed for As and Zn. Straw-char application significantly and noticeably decreased the plant transfer coefficients of Cd and Pb. This study, the first to investigate changes in metal mobility and iron plaque formation in rice plants due to amending a historically contaminated soil with biochar, indicates that biochar has a potential to decrease Cd, Zn and Pb accumulations in rice shoot but increase that of As. The main cause is likely biochar decreasing the C_pw of Cd and Zn, increasing the C_pw of As, and increasing the iron plaque blocking capacity for Cd and Pb.     

Diffusive gradients in thin films,Rhizon soil moisture samplers,and indicator plants to predict the bioavailabilities of potentially toxic elements in contaminated technosols

The phytoavailabilities and potential remobilization of potentially toxic elements (PTEs) such as Zn, Pb, Cd, As, and Sb were assessed in contaminated technosols from former mining and smelting sites. The PTE concentrations in soil pore water (SPW) and diffusive gradients in thin films (DGT)-measured concentration (C _DGT) methods were used to assess the bioavailabilities of PTE and their remobilization in this study. Together with classical Chelex-100 DGT probes to measure Zn, Cd, and Pb, novel ferrihydrite-backed DGT were used for As and Sb measurements alongside with Rhizon soil moisture sampler method for SPW sampling. To assess the phytoavailabilities of PTE, a germination test with dwarf beans as a plant indicator was used for this purpose. Dwarf bean primary leaves showed high Zn concentrations in contrast to Pb and Cd which showed low phytoavailabilities. Despite As and Sb are present in high concentrations in the mine tailings, their phytoavailabilities indicate very low bioavailabilities. The amounts of Zn, Pb, Cd, As, and Sb extracted with DGT devices correlated well with the total dissolved PTE concentrations in the SPW. The highest R values were observed for Zn, followed by Cd and Pb, indicating the ability of the soil to sustain SPW concentrations, which decreased in that order. Good correlations were also observed between each of dissolved PTE concentrations in SPW, DGT-measured PTE concentrations (C _DGT), and the accumulation of PTE in dwarf bean primary leaves. It could be concluded that the use of Rhizon soil moisture samplers and DGT methods may be considered to be a good methods to predict the PTE bioavailabilities in contaminated technosols.     

Grit ingestion as a source of metal exposure in the spruce grouse, Dendragapus canadensis

The objective of this study was to determine if ingestion of grit was a source of metal exposure to the spruce grouse, Dendragapus canadensis. A secondary objective was to assess whether grit could provide a supplemental source of essential minerals to their diet. Ca, P, Mg, S, Zn, Cu, Ni, Co, Cr, Fe, Mn, Al, Pb and Cd of liver (adult, yearling, chicks), crop and gizzard contents (adults) were determined for grouse collected from a relatively pristine boreal forest region of north-central Ontario, Canada. With the exception of Cd liver, concentrations were independent of age [one-way analysis of variance (ANOVA); p>0.004). Zn liver concentrations tended to be greater in adults than yearlings and chicks (one-way ANOVA; p=0.02). Liver concentrations of Cd increased with age (r=0.99; p<0.001). The contribution of crop items to total gizzard elemental content was element specific; crop contents contributed 90-100% of Mn and Zn, 70% for P and Ca, 60% for Pb, 50% for S, and 0-25% for Cu, Mg, Ni, Al, Fe, Co, Cr and Cd to the total elemental concentration of gizzard contents (crop plus grit). Incorporation of grit by grouse could, therefore, constitute an important source of essential macro-(Ca, P, Mg, S) and trace elements (Cu, Fe) but not for Mn or Zn. However, in addition to providing nutrients to the bird, ingestion of grit results in exposure to toxic trace metals such as Cd which in turn is accumulating in the liver. Research directed at determining grit turnover time, and hence metal exposure rates, in bird species which ingest grit to aid in food digestion is required. The toxicological significance of Cd exposure to grit-ingesting birds needs attention.     

Assessment of zerovalent iron for stabilization of chromium, copper, and arsenic in soil

Stabilization of soil contaminated with trace elements is a remediation practice that does not reduce the total content of contaminants, but lowers the amounts of mobile and bioavailable fractions. This study evaluated the efficiency of Fe(0) to reduce the mobility and bioavailability of Cr, Cu, As and Zn in a chromated copper arsenate (CCA)-contaminated soil using chemical, biochemical and biotoxicity tests. Contaminated soil was stabilized with 1% iron grit. This treatment decreased As and Cr concentrations in leachates (by 98% and 45%, respectively), in soil pore water (by 99% and 94%, respectively) and in plant shoots (by 84% and 95%, respectively). The stabilization technique also restored most of analyzed soil enzyme activities and reduced microbial toxicity, as evaluated by the BioTox test. After stabilization, exchangeable and bioaccessible fractions of Cu remained high, causing some residual toxicity in the treated soil.     

Phytostabilization of a metal contaminated sandy soil. I: Influence of compost and/or inorganic metal immobilizing soil amendments on phytotoxicity and plant availability of metals

In a lysimeter set-up, compost addition to an industrial contaminated soil slightly reduced phytotoxicity to bean seedlings. The "Phytotoxicity Index" (on a scale from 1 to 4) decreased from 3.5 to 2.8. The same treatment also reduced metal accumulation in grasses: mean Zn, Cd and Pb concentrations decreased respectively from 623 to 135, from 6.2 to 1.3 and from 10.7 to <6 mg kg-1 dry weight. When combined with inorganic metal immobilizing amendments, compost had a beneficial effect on plant responses additional to the inorganic amendments alone. Best results were obtained when using compost (C)+cyclonic ashes (CA)+steel shots (SS). The "Phytotoxicity Index" decreased to 1.7, highest diversity of spontaneously colonizing plants occurred, and metal accumulation in grasses reduced to values for uncontaminated soils. Based on the first year evaluation, C+CA+SS showed to be an efficient treatment for amendment assisted phytostabilization of the contaminated Overpelt soil.     

Phytostabilization of a metal contaminated sandy soil. II: Influence of compost and/or inorganic metal immobilizing soil amendments on metal leaching

A lysimeter approach (under natural climatologic conditions) was used to evaluate the effect of four metal immobilizing soil treatments [compost (C), compost+cyclonic ashes (C+CA), compost+cyclonic ashes+steel shots (C+CA+SS)) and cyclonic ashes+steel shots (CA+SS)] on metal leaching through an industrially contaminated soil. All treatments decreased Zn and Cd leaching. Strongest reductions occurred after CA+SS and C+CA+SS treatments (Zn: -99.0% and -99.2% respectively; Cd: -97.2% and -98.3% respectively). Copper and Pb leaching increased after C (17 and >30 times for Cu and Pb respectively) and C+CA treatment (4.4 and >3.7 times for Cu and Pb respectively). C+CA+SS or CA+SS addition did not increase Cu leaching; the effect on Pb leaching was not completely clear. Our results demonstrate that attention should be paid to Cu and Pb leaching when organic matter additions are considered for phytostabilization of metal contaminated soils.     

Heavy metal mobility in runoff water and absorption by eggplant fruits from sludge treated soil

Sewage sludge addition to agricultural lands requires judicious management to avoid environmental risks arising from heavy metal and nitrate contamination of surface water and accumulation in edible plants. A field study was conducted on a silty-loam soil of 10% slope at Kentucky State University Research Farm. Eighteen plots of 22 x 3.7 m each were separated using metal borders and the soil in six plots was mixed with sewage sludge and yard waste compost mix (SS-YW) at 15 t acre(-1), six plots were mixed with sewage sludge (SS) at 15 t acre(-1), and six unamended plots that never received sludge were used for comparison purposes. Plots were planted with eggplant, Solanum melongena L. as the test plant. The objectives of this investigation were to: 1) assess the effect of soil amendments on the transport of NO3, NH4, and heavy metals (Cd, Cr, Ni, Pb, Zn, Cu, and Mo) into surface water; 2) investigate the effect of soil amendments on heavy metal bioavailability in eggplant fruits at harvest; and 3) assess chemical and physical properties of soil following addition of soil amendments and their impact on the yield and quality of eggplant fruit. SS-YW treatments reduced runoff water by 63% while plots incorporated with sewage sludge alone reduced runoff water by 37% compared to control treatment. The SS-YW treatments transported more mineral nitrogen (NO3-N and NH4-N) in runoff water than SS treatments. Total marketable yield (lbs acre(-1)) and number of eggplant fruits were greatest in SS-YW treatments. This response may be due to improved soil porosity, water, and nutrient retention of the soil amended with SS-YW mixture. Concentrations of heavy metals in soil amended with sludge were below the U.S. Environmental Protection Agency (USEPA) limits. Chromium, Ni, Zn, and Cu were taken up by eggplant fruits but their concentrations were below the Codex Commission allowable levels.     

An inter-laboratory study to test the ability of amendments to reduce the availability of Cd, Pb, and Zn in situ

An international inter-laboratory research program investigated the effectiveness of in situ remediation of soils contaminated by cadmium, lead and zinc, measuring changes in soil and soil solution chemistry, plants and soil microbiota. A common soil, from mine wastes in Jasper County MO, was used. The soil was pH 5.9, had low organic matter (1.2 g kg(-1) C) and total Cd, Pb, and Zn concentrations of 92, 5022, and 18 532 mg kg(-1), respectively. Amendments included lime, phosphorus (P), red mud (RM), cyclonic ashes (CA), biosolids (BIO), and water treatment residuals (WTR). Both soil solution and NH4NO3 extractable metals were decreased by all treatments. Phytotoxicity of metals was reduced, with plants grown in P treatments having the highest yields and lowest metal concentration (0.5, 7.2 and 406 mg kg(-1) Cd, Pb, and Zn). Response of soil micro-organisms was similar to plant responses. Phosphorus addition reduced the physiologically based extraction test Pb from 84% of total Pb extracted in the untreated soil to 34.1%.     

Growth and trace metal accumulation of two Salix clones on sediment-derived soils with increasing contamination levels

The growth and metal uptake of two willow clones (Salix fragilis 'Belgisch Rood' and Salix viminalis 'Aage') was evaluated in a greenhouse pot experiment with six sediment-derived soils with increasing field Cd levels (0.9-41.4 mg kg-1). Metal concentrations of eight elements were measured in roots, stems and leaves and correlated to total and soil water metal concentrations. Dry weight root biomass, number of leaves and shoot length were measured to identify eventual negative responses of the trees. No growth inhibition was observed for both clones for any of the treatments (max. 41.4 mg kg-1 Cd, 1914 mg kg-1 Cr, 2422 mg kg-1 Zn, 655 mg kg-1 Pb), allowing their use for phytoextraction on a broad range of contaminated sediments. However, dry weight root biomass and total shoot length were significantly lower for S. viminalis compared to S. fragilis for all treatments. Willow foliar Cd concentrations were strongly correlated with soil and soil water Cd concentrations. Both clones exhibited high accumulation levels of Cd and Zn in aboveground plant parts, making them suitable subjects for phytoextraction research. Cu, Cr, Pb, Fe, Mn and Ni were found mainly in the roots. Bioconcentration factors of Cd and Zn in the leaves were highest for the treatments with the lowest soil Cd and Zn concentration.     

Enhanced phytoextraction of Cu, Pb, Zn and Cd with EDTA and EDDS

Chemically enhanced phytoextraction has been proposed as an effective approach to removing heavy metals from contaminated soil through the use of high biomass plants. Using pot experiments, the effects of the application of EDTA, EDDS and citric acid on the uptake of Cu, Pb, Zn and Cd by corn (Zea mays L. cv. Nongda 108) and bean (Phaseolus vulgaris L. white bean) plants were studied. The results showed that EDDS was more effective than EDTA at increasing the concentration of Cu in corn and beans. The application of 5 mmol kg-1 soil EDDS to soil significantly increased concentrations of Cu in shoots, with maximum levels of 2060 and 5130 mg kg-1 DW in corn and beans, respectively, which were 45- and 135-fold higher than that in the corresponding control plants to which chelate had not been applied. Concentrations of Zn in shoots were also higher in the plants treated with EDDS than in those treated with EDTA. For Pb and Cd, EDDS was less effective than EDTA. The maximum Cu phytoextraction was found with the EDDS treatment. The application of EDTA and EDDS also significantly increased the shoot-to-root ratios of the concentrations of Cu, Pb, Zn and Cd in both plant species. The results of metal extraction with chelates showed that EDDS was more efficient at solubilizing Cu and Zn than EDTA, and that EDTA was better at solubilizing Pb and Cd than EDDS.     

Distribution of seven heavy metals among hot pepper plant parts

The main objective of this investigation was to monitor concentrations of seven metals (Cd, Pb, Ni, Mo, Cu, Zn, and Cr) in the fruits, leaves, stem, and roots of Capsicum annuum L. (cv. Xcatic) plants grown under four soil management practices: yard waste (YW), sewage sludge (SS), chicken manure (CM), and no-much (NM) bare soil. Elemental analyses were conducted using inductively coupled plasma mass spectrometer. Pb and Cd concentrations in soil amended with YW, SS, and CM were not significantly different (P < 0.05) compared to NM soil, whereas Mo and Cu concentrations were significantly greater in YW compared to SS, CM, and NM treatments. Concentrations of Cd in the fruits of plants grown in NM soil were greater compared to the fruits of plants grown in other treatments. Total Ni concentration (sum of Ni in all plant parts) in plants grown in NM bare soil was greater than in plants grown in SS-, YW-, and CM-amended soils. Values of the bioaccumulation factor indicated that pepper fruits of plants grown in YW, SS, and CM did not show any tendency to accumulate Pb, Cr, and Ni in their edible fruits.     

Long-term effects of aided phytostabilisation of trace elements on microbial biomass and activity, enzyme activities, and composition of microbial community in the Jales contaminated mine spoils

We studied the effectiveness of remediation on microbial endpoints, namely microbial biomass and activity, microbial and plant species richness, of an As-contaminated mine spoil, amended with compost (C) alone and in combination with beringite (B) or zerovalent iron grit (Z), to increase organic matter content and reduce trace elements mobility, and to allow Holcus lanatus and Pinus pinaster growth. Untreated spoil showed the lowest microbial biomass and activity and hydrolase activities, and H. lanatus as sole plant species, whereas the presented aided phytostabilisation option, especially CBZ treatment, significantly increased microbial biomass and activity and allowed colonisation by several plant species, comparable to those of an uncontaminated sandy soil. Microbial species richness was only increased in spoils amended with C alone. No clear correlation occurred between trace element mobility and microbial parameters and plant species richness. Our results indicate that the choice of indicators of soil remediation practices is a bottleneck.     

Effects of EDTA and low molecular weight organic acids on soil solution properties of a heavy metal polluted soil

A pot experiment was conducted to study the effects of EDTA and low molecular weight organic acids (LMWOA) on the pH, total organic carbon (TOC) and heavy metals in the soil solution in the rhizosphere of Brassica juncea grown in a paddy soil contaminated with Cu, Zn, Pb and Cd. The results show that EDTA and LMWOA have no effect on the soil solution pH. EDTA addition significantly increased the TOC concentrations in the soil solution. The TOC concentrations in treatments with EDTA were significantly higher than those in treatments with LMWOA. Adding 3 mmol kg(-1) EDTA to the soil markedly increased the total concentrations of Cu, Zn, Pb and Cd in the soil solution. Compared to EDTA, LMWOA had a very small effect on the metal concentrations. Total concentrations in the soil solution followed the sequence: EDTA > citric acid (CA) approximately oxalic acid (OA) approximately malic acid (MA) for Cu and Pb; EDTA > MA > CA approximately OA for Zn; and EDTA > MA > CA > OA for Cd. The labile concentrations of Cu, Zn, Pb and Cd showed similar trends to the total concentrations.     

Eisenia fetida avoidance behavior as a tool for assessing the efficiency of remediation of Pb, Zn and Cd polluted soil

Remediation by means of soil leaching with ethylenediaminetetraacetic acid (EDTA) is capable of extracting the most labile soil fractions, leaving the residual metals in biologically non-available forms. We evaluated the feasibility of the standardized earthworm (Eisenia fetida) avoidance test for assessing the efficiency of soil remediation of Pb, Zn and Cd polluted soil. Chemical extraction tests (six-step sequential extraction, toxicity characteristic leaching procedure, physiologically based extraction test, diethylenediaminepentaacetic acid extraction) indicated that the mobility, oral bioaccessibility and phytoavailability of Pb, Zn and Cd were consistently reduced. However, the avoidance test showed no significant avoidance of polluted soil in favor of that which had been remediated. Pb, Zn and Cd accumulation in E. fetida mirrored the decreasing pattern of metal potential bioavailability gained by leaching the soil with increasing EDTA concentrations. The calculated bioaccumulation factors indicated the possibility of underestimating the metal bioavailability in soil using chemical extraction tests.