Influence of population density on the concentration and speciation of metals in the soil and street dust from urban areas.

Street dust and soil from high, medium and low populated cities and natural area were analysed for selected physical-chemical properties, total and chemical speciation of Zn, Pb, Cu, Cr, Cd, Co, Ni to understand the influence of human activities on metal accumulation and mobility in the environment. The pH, salinity, carbonates and organic carbon contents were similar between soil and dust from the same city. Population density increases dust/soil salinity but has no influence on metals concentrations in soils. Increases in metal concentrations with population density were observed in dusts. Cu, Zn, Pb, Cr can be mobilized more easily from dust compared to the soil. In addition, population density increase the percentage of Pb and Zn associated to reducible and carbonate phase in the dust. The behaviour of metals except Cd in soil is mainly affected by physico-chemical properties, while total metal influenced the speciation except Cr and Ni in dusts.

Syrian bean-caper (Zygophyllum fabago L.) improves organic matter and other properties of mine wastes deposits.

The omni-presence of Zygophyllum fabago L. (Syrian bean-caper) natural colonies in post mining areas prompted us to investigate its contributions to reclamation of mine wastes deposits in southeast Spain. Select plant-related (edaphic) characteristics and bio- and water soluble-Cd, Cu, Pb and Zn in rhizosphere of Z. fabago were compared to deposits one year since application of pig slurry and marble waste. Total N in rhizosphere increased up to a factor of 20X (339 vs 17 mg N kg(-1)) in El Gorguel and 27X (85 vs 3.1 mg N kg(-1)) in El Lirio sites. Organic matter accumulation in rhizosphere from litter and roots of Z. fabago increased organic C from 6.6 to 19.5 g kg(-1) in El Gorguel and from 2.1 to 5.7 g kg(-1) in El Lirio in one year. Dissolution of inorganic C takes place due to organic acids from root exudates of Z. fabago. Reduction in bio-available Cd, Cu, Pb, and Zn in rhizosphere of Z. fabago at El Lirio is attributed to increase in pH from 5.3 to 7.7 through marble waste addition, although increased cation exchange capacity may also have played a role. Addition of marble waste to encourage colonization by Z. fabago in acidic mine wastes deposits was recommended.

Marble wastes and pig slurry improve the environmental and plant-relevant properties of mine tailings.

Poor soil fertility is often the biggest challenge to the establishment of vegetation in mine wastes deposits. We conducted field trials in the El Gorguel and El Lirio sites in SE Spain, two representative tailing ponds of similar properties except for pH, to understand the environmental and plant-relevant benefits of marble waste (MW) and pig slurry (PS) applications to mine tailings. Low pH (5.4) tailings (El Lirio) exhibit reduction of up to fourfold in bio-availability of metals as shown by the DTPA-Zn, Pb, water-soluble Zn, Pb and up to 3× for water-soluble Cd. Tailings in El Gorguel have high pH (7.4) and did not exhibit significant trends in the reductions of water-extractable Zn, Pb, Cd and Cu. Improvements to the edaphic (plant-relevant) properties of tailings after the amendments are not as sensitive to pH compared to the environmental characteristics. The two sites had increases in aggregate stability, organic matter (total N and organic C) although total N is higher in the El Gorguel (up to 212 µg N kg(-1)) than the El Lirio (up to 26 µg N kg(-1)). However, cation exchange capacities are similar in both sites at 15.2 cmol(+) kg(-1). We conclude that the characteristics, especially pH, of tailing materials significantly influence the fate of metals but not improvements to plant-relevant properties such as cation exchange capacity and aggregate stability 1 year after the application of MW and PS amendments.

Organic acids inhibit the formation of pyromorphite and Zn-phosphate in phosphorous amended Pb- and Zn-contaminated soil.

Pyromorphite (PY) and some zinc phosphates (Zn-P) are very sparingly soluble minerals and hence can immobilize Pb and Zn in contaminated soils. However, mechanisms leading to the poor efficiency of PY and Zn-P formation in contaminated soils amended with P still remain unclear. We studied the influence of two low molecular weight organic acids (LMWOA) - oxalic acid and citric acid and diethylene triamine pentaacetic acid (DTPA) - in PY and Zn-P formation in a P-amended contaminated soil. Despite the high levels of metals (∼4% Pb and 21% Zn) in the study soil, the addition of up to 1% inorganic P transformed only up to 37% and 17% of the total Pb and Zn to PY and Zn-P, respectively. Semi-quantitative estimates from a linear combination fitting of X-ray absorption near edge spectra (LC-XANES fitting) showed that the formation of PY decreased from 37% to 3% of the total Pb in the presence of oxalic acid and the addition of 1% P. The reduced PY formation may be associated with the increase in organic-bound Pb from 9% to 54% and decrease in carbonate associated Pb from 42% to 12% with oxalic acid addition as indicated by a chemical sequential extraction (SE) technique. Citric acid seemed to have a less adverse effect in PY formation than oxalic acid. Our data also suggests both oxalic and citric acids have less adverse effects on the efficiency of Zn-P formation. From this study we conclude that the abundance of LMWOA in soil environments can be one factor contributing to the poor efficiency of P amendments practices to effectively immobilize Pb and Zn in metal contaminated soils.

Uptake of phosphorus and lead by Brassica juncea and Medicago sativa from chloropyromorphite.

In situ remediation of lead (Pb)-contaminated soils via phosphate amendments has been extensively used to immobilize Pb as pyromorphite. However, in phosphorus (P) deficient soils, plants may develop extensive root systems to access P in any P-containing minerals, thereby affecting the stability of Pb5 (PO4)3Cl (Chloropyromorphite; CP). We grew Brassica juncea and Medicago sativa in sand culture to evaluate the stability of CP in the presence or absence of hydroxyapatite (HA) as P source. Treatments (per kilogram of sand) watered with P-nutrient solution were control [PC0, (without CP)], 1, and 5 g Pb as CP [PC1, and PC5] and 0.45 g P as HA (PA), and those of watered with P-free nutrient solution were 1 and 5 g Pb as CP [NC1 and NC5], 5 g Pb as CP plus 0.45 g P as HA [NAC5], and 0.45 g P as HA [NA]. Plants in NC1 and NC5 treatments showed stunted growth and reductions in shoot elongation and leaf size. Among CP treated pots, the highest shoot Pb uptake was observed in NAC5 treatment. The results suggested that Pb accumulation and translocation in the plants was markedly higher in P-sufficient conditions than in P-deficient conditions.

Organic acid-induced release of lead from pyromorphite and its relevance to reclamation of Pb-contaminated soils.

The long-term stability of pyromorphite [Pb(5)(PO(4))(3)Cl] (PY) in root-soil interface (or rhizosphere) where production of organic acids from biological activities takes place is not fully understood. We conducted a 1-year long laboratory batch dissolution experiment to elucidate the release of Pb (and P) from PY by four commonly occurring low molecular weight organic acids (LMWOA) in rhizosphere: acetic, citric, malic and oxalic acid. Mean maximum amount of Pb in milliQ (mQ) water (1.8microM) was lower than in solutions from LMWOA alone or in combination with each other (i.e., mixed acid). However, there was no significant difference in the amount of Pb (and P) in solution in all treatments including mQ water after 6months. Among the 100microM LMWOA, mean of five highest soluble Pb (muM Pb in solution) followed the order: oxalic acid (17.6)>citric (6.2)>malic (5.6)>acetic acid (3.0microM Pb). Mixed acid solution had a maximum amount of 14.0microM Pb. We calculated a range of solubility product constant (K(sp)) of PY in this study from 8.6x10(-54) (mQ) to 7.0x10(-45)(oxalic acid); these values are within the range of PY K(sp) reported elsewhere. Despite the low K(sp) values, LMWOA-induced released Pb from PY are in concentrations higher than both Canadian and international drinking water and agricultural water use quality standards. This suggests that soil organic acids such as in rhizosphere can potentially liberate Pb from PY in contaminated soils.

Soil organic matter from pioneer species and its implications to phytostabilization of mined sites in the Sierra de Cartagena (Spain).

Pioneer plant species were observed growing on mined areas despite unfavourable conditions such as extreme pH, high salinity and phytotoxic levels of several elements. This study evaluated the contribution of pioneer species to the accumulation of soil organic matter (SOM). We collected 51 samples from 17 non-vegetated, natural and pioneer-vegetated sites in five highly saline mined areas in the Sierra de Cartagena (Spain). The composition of SOM was determined using total C, N and S elemental anlayzer, pyrolysis and solid state (13)C NMR spectroscopy. Results showed that pioneer species like Lygeum spartum had contributed approximately 11 kg SOM kg(-1) soil into the Balsa Rosa sites since 1991; it will take approximately 120 years of continuous growth for this plant to increase the SOM level comparable to natural site. In the Portman Bay area, Sarconia ramosissima and Phragmites australis can contribute SOM equivalent to present day SOM in natural sites in the next 30 years. Low quality SOM (C/N>20) deposited by pioneer plants was dominated by lignin-derived organic compounds such as phenols, guaiacols, syringols and aromatics while polyssacharides and alkyls were the major components in high quality SOM (C/N<20). The addition of SOM to mine wastes is similar to early stages of soil formation and with time, we expect the formation of well-developed Ah horizon on the surface of mine wastes. The presence of P. australis on several sites makes it a very good candidate for successful revegetation of hostile conditions found in many mined sites.

Uptake, distribution, and speciation of chromium in Brassica juncea.

Brassica juncea (Indian mustard) has been widely used in phytoremediation because of its capacity to accumulate high levels of chromium (Cr) and other metals. The present study was conducted to investigate mechanism(s) involved in Cr binding and sequestration by B. juncea. The plants were grown under greenhouse conditions in field-moist or air-dried soils, amended with 100 mg kg(-1) of Cr (III) or VI). The plant concentrated Cr mainly in the roots. B. juncea removed an average of 48 and 58 microg Cr per plant from Cr (III) and Cr (VI)-treated soils, respectively. The uptake of Cr was not affected by the moisture status of the soils. X-ray absorption near-edge spectroscopy measurements showed only Cr (III) bound predominantly to formate and acetate ligands, in the bulk and rhizosphere soils, respectively. In the plant tissues, Cr (III) was detected, primarily as acetate in the roots and oxalate in the leaves. X-ray microprobe showed the sites of Cr localization, and probably sequestration, in epidermal and cortical cells in the roots and epidermal and spongy mesophyll cells in the leaves. These findings demonstrate the ability of B. juncea to detoxify more toxic Cr (VI), thereby making this plant a potential candidate for phytostabilization.

Properties of hydrocarbon- and salt-contaminated flare pit soils in northeastern British Columbia (Canada).

Many contaminated sites in Canada are associated with flare pits generated during past petroleum extraction operations. Flare pits are located adjacent to well sites, compressor stations and batteries and are often subjected to the disposal of wastes from the flaring of gas, liquid hydrocarbons and brine water. This study was conducted to evaluate the physical, chemical, electrical and mineral properties of three flare pit soils as compared to adjacent control soils. Results showed that particle size distribution, pH, total N, cation exchange capacity, exchangeable Mg(2+), and sodium adsorption ratio were similar in soils from flare pits and control sites. Total C, exchangeable Ca(2+), K(+) and Na(+), soluble Ca(2+), Mg(2+), K(+) and Na(+) and electrical conductivity were higher in flare pit soils compared to control soils. X-ray diffraction and scanning electron microscopic analyses showed the presence of gypsum [CaSO(4).2H(2)O], dolomite [CaMg(CO(3))(2)], pyrite [FeS(2)], jarosite [KFe(3)(OH)(6)(SO(4))(2)], magnesium sulphate, oxides of copper and iron+copper in salt efflorescence observed in flare pit soils. Soils from both flare pits and control sites contained mica, kaolonite and 2:1 expanding clays. The salt-rich materials altered the ionic equilibria in the flare pit soils; K(Mg-Ca) selectivity coefficients in control soils were higher compared to contaminated soils. The properties of soils (e.g., high electrical conductivity) affected by inputs associated with oil and gas operations might render flare pit soils less conducive to the establishment and growth of common agricultural crops and forest trees.

Evaluation of iron-phosphate as a source of internal lake phosphorus loadings.

Biological, physical and chemical characteristics of the water column of a shallow (Zmax = 9.2 m), small (surface area 3.8 km2) residential and recreational lake near Prince George, British Columbia, indicated that the system was being loaded internally with phosphorus (P) from the sediments. The abundance of P released from the fine glaciolacustrine, and organic rich sediments was resulting in excess algal and weed growth. It was postulated that iron-phosphate reduction at redox potentials below approximately 200 mV and/or bacterially mediated orthophosphate (PO4-P) releases could be occurring. The development of an appropriate nutrient management strategy required that the process associated with the sediment P release be determined. The MINTEQA2 geochemical model was used to predict the release of orthophosphate (PO4-P) into the interstitial water with the assumption that P is present alternately as strengite, variscite and hydroxyapatite. The predicted release of PO4-P from these P containing minerals was compared to the concentration of PO4-P and total phosphorus (TP) in the overlying hypolimnion. In order to improve the accuracy of the model prediction, the proportion of the sediment present as iron-bound phosphate was estimated. A significant correlation between the observed hypolimnetic TP and interstitial PO4-P concentrations as predicted from iron-bound P dissolution (r2 = 0.59) was found. Total phosphorus release rates to the hypolimnion were also found to be strongly correlated to the iron-bound P component of the sediment (r2 = 0.88). Multivariate regression analyses showed significant relationships between hypolimnetic PO4-P and sediment iron-bound P, Eh, and interstitial Fe (r2 = 0.76). These results provided sufficient evidence to conclude that PO4-P in the system is predominantly bound to Fe-containing minerals and therefore could be managed using treatment techniques that address iron-bound phosphates.

Radon emanation coefficients for phosphogypsum.

Phosphogypsum is a by-product of the phosphate fertilizer industry which is stockpiled in large quantities world-wide. Phosphogypsum consists mainly of dihydrate gypsum (CaSO42H2O) but also contains elevated concentrations of 226Ra and other inorganic species which originate from the processing of phosphate rock. 222Rn gas is the first decay product of 226Ra and has been identified as one of the major environmental concerns associated with phosphogypsum. This study was conducted to determine effects of particle size, weathering, and moisture content on the 222Rn emanation coefficient (epsilon) for phosphogypsum. Average epsilon for air-dry, unfractionated phosphogypsums derived from Togo, Florida, or Idaho rock was approximately 12%. Average epsilon for fine fraction phosphogypsum (< 20 microns diameter) was greater than for unfractionated phosphogypsum by a factor of 4.6, 1.4, and 4.4 for samples derived from Idaho rock, Togo rock, and Florida rock, respectively. Phosphogypsum samples subjected to an artificial weathering procedure lost 40% mass, with no change in epsilon. Increasing water content was found to first slightly decrease, then to increase epsilon compared to air-dry samples; epsilon for 100% saturated phosphogypsum was 1.9-fold greater than in air-dry phosphogypsum. Particle size sorting could account for variability of 222Rn exhalation at repositories. Very high moisture contents could slightly increase 222Rn emanation, but exhalation would likely be reduced due to slow diffusion through porosity of saturated phosphogypsum.