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.     

Ionic strength effects in biosorption of metals by marine algae

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

Separation of toxaphene by high resolution gas chromatography

A summary is given about the separation of toxaphenes by high resolution gas chromatography (HRGC). The suitability of different stationary phases for isomer and/or enantiomer-selective separations is compared. Multidimensional and tandem techniques are also presented. In addition, problems caused by thermal degradation in the injector and on the column are addressed. Furthermore, a brief survey is included about detection methods such as electron capture detection and different mass spectrometric methods.     

Toxaphene in standard solutions and cleaned biota extracts--results of the first QUASIMEME interlaboratory studies. Quality Assurance of Information for Marine Environmental Monitoring in Europe

Two interlaboratory studies on individual toxaphene congeners have been organised by the project Quality Assurance of Information for Marine Environmental Monitoring in Europe (QUASIMEME). Fifteen laboratories analysed two standard solutions in the first study and 13 laboratories analysed a standard solution and two cleaned biota extracts in the second study. The coefficients of variation obtained for the standard solutions were 6-21% and for the cleaned extracts 16-39%. Although the results were comparable to those of other studies, further improvement in the level of agreement between the participating laboratories was considered possible.     

Priority assessment of toxic substances in life cycle assessment. Part I: calculation of toxicity potentials for 181 substances with the nested multi-media fate, exposure and effects model USES-LCA

Toxicity potentials are standard values used in life cycle assessment (LCA) to enable a comparison of toxic impacts between substances. In most cases, toxicity potentials are calculated with multi-media fate models. Until now, unrealistic system settings were used for these calculations. The present paper outlines an improved model to calculate toxicity potentials: the global nested multi-media fate, exposure and effects model USES-LCA. It is based on the Uniform System for the Evaluation of Substances 2.0 (USES 2.0). USES-LCA was used to calculate for 181 substances toxicity potentials for the six impact categories freshwater aquatic ecotoxicity, marine aquatic ecotoxicity, freshwater sediment ecotoxicity, marine sediment ecotoxicity, terrestrial ecotoxicity and human toxicity, after initial emission to the compartments air, freshwater, seawater, industrial soil and agricultural soil, respectively. Differences of several orders of magnitude were found between the new toxicity potentials and those calculated previously.     

Natural products: seasonal variation in trichome counts and contents in Lycopersicum hirsutum f. glabratum

Wild tomato leaves possess a pest-resistance mechanism in their glandular trichomes and the exudates they produce. Type IV and VI glandular trichomes on the leaves of five wild tomato accessions of Lycopersicum hirsutum f. glabratum (PI 126449, PI 134417, PI 134418, PI 251304, and LA 407) grown under greenhouse conditions were counted. Major chemical compounds from glandular leaf trichomes of the accessions tested were extracted, purified, and quantified at different periods during the growing seasons by gas chromatography (GC) and mass spectrometry (GC/MS). The toxicity of two methylketones (2-undecanone and 2-tridecanone), the major constituents of the accessions tested, to adults of the sweetpotato whitefly, Bemisia tabaci (Gennadius) and fourth instar larvae of the Colorado potato beetle (CPB), Leptinotarsa decemlineata (Say), was determined using no-choice bioassays. 2-undecanone caused 80% mortality of the fourth instar larvae of the CPB at the highest concentration tested (100 mg 2-undecanone mL(-1) of acetone) while 2-tridecanone caused 72% mortality of whiteflies at 20 mg 2-tridecanone mL(-1) of 65% ethanol. The concentration of 2-undecanone and 2-tridecanone on the leaves of each of the five accessions of L. hirsutum f. glabratum and the mass spectra of 2-undecanone and 2-tridecanone are presented. Overall, the concentration of 2-undecanone on the leaves was significantly higher than 2-tridecanone. Concentration of the two methylketones varied among accessions and sampling season. Plants produced the highest concentration of 2-undecanone during the month of August. On average, each plant of accession PI 251304 provided 354 g fresh leaves (averaging about 52,353 cm2 exposed leaf surface area) and produced 32.5 and 8.7 mg of 2-undecanone and 2-tridecanone, respectively. L. hirsutum f. glabratum accessions may become a valuable source of natural products, which could minimize reliance on synthetic pesticides.     

Screening of organic halogens and identification of chlorinated benzoic acids in carbonaceous meteorites

The occurrence of halogenated organic compounds measured as a sum parameter and the evidence of chlorinated benzoic acids in four carbonaceous meteorites (Cold Bokkeveld, Murray, Murchison and Orgueil) from four independent fall events is reported. After AOX (Adsorbable organic halogen) and EOX (Extractable organic halogen) screening to quantify organically bound halogens, chlorinated organic compounds were analyzed by gas chromatography. AOX concentrations varying from 124 to 209 microg Cl/g d.w. were observed in carbonaceous meteorites. Ion chromatographic analysis of the distribution of organically bound halogens performed on the Cold Bokkeveld meteorite revealed that chlorinated and brominated organic compounds were extractable, up to 70%, whereas only trace amounts of organofluorines could be extracted. Chlorinated benzoic acids have been identified in carbonaceous meteorite extracts. Their presence and concentrations raise the question concerning the origin of halogenated, especially chlorinated, organic compounds in primitive planetary matter.     

Photodegradation of pentachlorophenol and its degradation pathways predicted using density functional theory

The objectives of the present research were (i) to report the mass balance of chlorine during pentachlorophenol (PCP) photodegradation and (ii) to reveal the photodegradation pathway experimentally with a theoretical proof based on the density functional theory (DFT). The chlorine of PCP was completely mineralized to produce chloride ions after 24h of UV irradiation. As intermediates, 2,3,5,6-tetrachlorophenol, 2,3,4,6-tetrachlorophenol and 2,5-dichlorophenol were identified. At least 80% of the chlorine balance during PCP photodegradation was accounted by PCP, these intermediates, and chloride ions. A DFT calculation showed differences in the C-Cl bond dissociation energy level and the positions of respective PCP molecular and the PCP intermediates. The dechlorination intermediates predicted using the calculated C-Cl bond dissociation energy were consistent with those experimentally confirmed, indicating the feasibility of this theoretical method in predicting the dechlorination pathway.     

Anaerobic degradation of hexachlorocyclohexane isomers in liquid and soil slurry systems

Gamma-hexachlorocyclohexane (gamma-HCH or lindane), one of the most commonly used insecticides, has been mainly used in agriculture. Organochloride compounds are known to be highly toxic and persistent, causing serious water and soil pollution. The objective of the present study is the evaluation of the anaerobic degradation of alpha-, beta-, gamma-, delta-HCH in liquid and slurry cultures. The slurry system with anaerobic sludge appears as an effective alternative in the detoxification of polluted soils with HCH, as total degradation of the four isomers was attained. While alpha- and gamma-HCH disappeared after 20-40d, the most recalcitrant isomers: beta- and delta-HCH were only degraded after 102d. Intermediate metabolites of HCH degradation as pentachlorocyclohexane (PCCH), tetrachlorocyclohexene (TCCH), tri-, di- and mono-chlorobenzenes were observed during degradation time.     

Potential of Brassic rapa, Cannabis sativa, Helianthus annuus and Zea mays for phytoextraction of heavy metals from calcareous dredged sediment derived soils

Remediation of soil pollution is one of the many current environmental challenges. Anthropogenic activity has resulted in the contamination of extended areas of land, the remediation of which is both invasive and expensive by conventional means. Phytoextraction of heavy metals from contaminated soils has the prospect of being a more economic in situ alternative. In addition, phytoextraction targets ecotoxicologically the most relevant soil fraction of these metals, i.e. the bioavailable fraction. Greenhouse experiments were carried out to evaluate the potential of four high biomass crop species in their potential for phytoextraction of heavy metals, with or without with the use of soil amendments (EDTA or EDDS). A calcareous dredged sediment derived surface soil, with high organic matter and clay content and moderate levels of heavy metal pollution, was used in the experiments. No growth depression was observed in EDTA or EDDS treated pots in comparison to untreated controls. Metal accumulation was considered to be low for phytoextraction purposes, despite the use of chelating agents. The low observed shoot concentrations of heavy metals were attributed to the low phytoavailability of heavy metals in this particular soil substrate. The mobilising effects induced by EDTA in the soil were found to be too long-lived for application as a soil amendment in phytoextraction. Although EDDS was found to be more biodegradable, higher effect half lives were observed than reported in literature or observed in previous experiments. These findings caution against the use of any amendment, biodegradable or otherwise, without proper investigation of its effects and the longevity thereof.