Antimony bioavailability in mine soils

Five British former mining and smelting sites were investigated and found to have levels of total Sb of up to 700 mg kg(-1), indicating high levels of contamination which could be potentially harmful. However, this level of Sb was found to be biologically unavailable over a wide range of pH values, indicating that Sb is relatively unreactive and immobile in the surface layers of the soil, remaining where it is deposited rather than leaching into lower horizons and contaminating ground water. Sb, sparingly soluble in water, was unavailable to the bacterial biosensors tested. The bioluminescence responses were correlated to levels of co-contaminants such as arsenic and copper, rather than to Sb concentrations. This suggests that soil contamination by Sb due to mining and smelting operations is not a severe risk to the environment or human health provided that it is present as immobile species and contaminated sites are not used for purposes which increase the threat of exposure to identified receptors. Co-contaminants such as arsenic and copper are more bioavailable and may therefore be seen as a more significant risk.     

Multivariate statistical study of heavy metal enrichment in sediments of the Pearl River Estuary

The concentrations and chemical partitioning of heavy metals in the sediment cores of the Pearl River Estuary were studied. Based on Pearson correlation coefficients and principal component analysis results, Al was selected as the concentration normalizer for Pb, while Fe was used as the normalizing element for Co, Cu, Ni and Zn. In each profile, sections with metal concentrations exceeding the upper 95% prediction interval of the linear regression model were regarded as metal enrichment layers. The heavy metal accumulation mainly occurred at sites in the western shallow water areas and east channel, which reflected the hydraulic conditions and influence from riparian anthropogenic activities. Heavy metals in the enrichment sections were evaluated by a sequential extraction method for possible chemical forms in sediments. Since the residual, Fe/Mn oxides and organic/sulfide fractions were dominant geochemical phases in the enriched sections, the bioavailability of heavy metals in sediments was generally low. The 206Pb/207Pb ratios in the metal-enriched sediment sections also revealed the influence of anthropogenic sources. The spatial distribution of cumulative heavy metals in the sediments suggested that the Zn and Cu mainly originated from point sources, while the Pb probably came from non-point sources in the estuary.     

AFLP analysis as biomarker of exposure to organic and inorganic genotoxic substances in plants

In recent years several plant species have been in use as bioindicators and several tests have been developed to evaluate the toxicity of environmental pollutants in vegetal organisms. In the present paper Arabidopsis thaliana (L.) Heynh. (ecotype Wassilewskija) was used as bioindicators of two genotoxic substances: potassium dichromate and dihydrophenanthrene. Inhibition of seed germination was observed with both pollutants. AFLP analysis (i) indicated that both substances are genotoxic, (ii) showed that dihydrophenanthrene induces DNA changes in different target sequences than potassium dichromate, (iii) quantified the genotoxic effect using cluster analysis by comparing DNA from treated plants with that of control plants. On the basis of these considerations we suggest that AFLP method is a powerful tool for measuring qualitative and quantitative genotoxic activity due to environmental pollutants. AFLP method can be applied to a wide range of bioindicator organisms and may become a universal methodology to identify target genes for specific genotoxic agents. This could open up possibilities for designing specifically targeted assays and new approaches to risk assessment.     

Geochemical evidences of the anthropogenic alteration of trace metal composition of the sediments of Chiricahueto marsh (SE Gulf of California)

Seven sediment cores (60-80 cm) were collected at Chiricahueto marsh, a salt marsh influenced by agrochemical, domestic and industrial effluents. The concentrations of Ag, Al, Cd, Co, Cu, Fe, Li, Mn, Pb, V and Zn were studied in the solid phase at each 1-cm section. The profiles of Ag, Cd, Cu, Mn, Ni, Pb and Zn showed a slight recent pollution in the site with enrichment and anthropogenic factors higher than unity; and correlation analysis indicated a direct association with organic carbon. Al, Co, Cr, Fe, Li, and V concentration profiles displayed a negative correlation with organic C and positive with mud content and no consistent enrichment at surface. Based on the principal component analysis and correlation analysis, two principal groups of metals were identified. The first group includes Al, Co, Cr, Fe and Li, that are derived predominantly from the weathering of parent materials in the local bedrock; and the second group include most of the metals, which were relatively enriched at surficial sediments, that are produced mainly by anthropogenic activities such as agriculture (Cd, Cu and Zn), sewage effluents (Ag, Cd, Cu, Ni, Pb and Zn) and in lesser extent atmospheric deposition (Cd and Pb).     

Basic processes in phytoremediation and some applications to air pollution control

In this short review, basic processes for phytoremediation and plant enzymes that are potentially useful in phytoremediation are briefly summarized. The remaining part describes the applications of the basic processes to decontaminate pollutants in the environments that have been done in our laboratory. Our work includes (1) analysis of the capability of various naturally occurring plants to decontaminate atmospheric nitrogen dioxide and selection of nitrogen-dioxide-philic plants that grow with nitrogen dioxide as the sole nitrogen source, (2) production of transgenic plants to improve plants' capability to decontaminate atmospheric nitrogen dioxide, and (3) analysis of the denitrification process in plants to innovate a gas--gas-converting plants that convert nitrogen dioxide to nitrogen gas.     

Plant uptake and translocation of air-borne chlordane and comparison with the soil-to-plant route

In order to assess fully the impact of persistent organic pollutants (POPs) on human health, pollutant exchange at the interface between terrestrial plants, in particular food crops, and other environmental compartments must be thoroughly understood. In this regard, transfers of multicomponent and chiral pollutants are particularly informative. In the present study, zucchini (Cucurbita pepo L.) was planted in containerized, uncontaminated soil under both greenhouse and field conditions and exposed to air-borne chlordane contamination at 14.0 and 0.20 ng/m(3) (average, greenhouses), and 2.2 ng/m(3) (average, field). Chiral gas chromatography interfaced to an ion trap mass spectrometer was used to determine the chiral (trans-chlordane, TC, and cis-chlordane, CC) and achiral (trans-nonachlor, TN) chlordane components in vegetation, air, and soil compartments. The chlordane components of interest were detected in all vegetation tissues examined--root, stem, leaves, and fruits. When compared with the data from a soil-to-plant uptake study, the compositional profile of the chlordane components, i.e. the component fractions of TC, CC, and TN, in plant tissues, showed significantly different patterns between the air-to-plant and soil-to-plant pathways. Changes in the enantiomer fractions of TC and CC in plant tissues relative to the source, i.e. air or soil, although observed, were not markedly different between the two routes. This report provides the first comprehensive comparison between two distinct plant uptake routes for POPs and their subsequent translocation within plant tissues.     

Investigation of organic xenobiotic transfers,partitioning and processing in air-soil-plant systems using a microcosm apparatus. Part II: comparing the fate of chlorobenzenes in grass planted soil

A microcosm system was used to investigate and compare transfers of 14C labeled-1,2-dichlorobenzene (DCB), 1,2,4-trichlorobenzene (TCB) and hexachlorobenzene (HCB) in an air-soil-plant system using single grass tillers planted into spiked soil. This study was the second phase of a development investigation for eventual study of a range of xenobiotic pollutants. Recoveries from the system were excellent at >90%. The predominant loss pathway for 14C labeled-1,2-DCB and 1,2,4-TCB was volatilisation with 85% and 76% volatilisation of parent compound and volatile metabolites over 5 weeks respectively. Most of the added label in the hexachlorobenzene spiked system remained in soil. Mineralisation was <1% for all compounds. 14C plant burdens expressed as microg parent compound/g plant fresh weight were significant and suggest that plant uptake of chlorobenzenes from soil may be an important exposure pathway for grazing herbivores. Both shoot and root uptake of 14C was detected, with foliar uptake of volatilised compounds dominating shoot uptake, and being greatest in TCB spiked systems. The microcosm is shown as potentially an ideal system with which to investigate organic xenobiotic partitioning in air-soil-plant systems to improve understanding of the equilibria and kinetics of exchanges. However, limitations imposed by the lab based conditions must be recognized and data should be compared with field based data sets as a consequence.     

Investigation of various physicochemical and environmental parameter influence on pesticide sorption to ditch bed substratum by means of experimental design

Diffuse pollution by pesticide applied in rural catchments may contribute to alter water quality. Besides actions relative to the way the substances are introduced into the environment, it is also possible to limit the contamination by interfering on their transfer pathways from fields to the main river network. Especially, interface areas such as buffer strips or small ditches may play a major part in pesticide diffuse pollution decrease. In ditches a great variety of materials may act as sorbents for organic contaminants: grass, leaves, wood debris or sediments. In this study, laboratory experiments were designed to determine sorption characteristics for three herbicides with different physicochemical properties on sediment and leaves in decay commonly found in agricultural ditches. Sorption capacities were assessed for the herbicides isoproturon, diuron and diflufenican.

Experimental design was carried out to investigate the effects of five parameters on herbicide sorption on sediment and dead leaves. These parameters have been chosen according to parallel field experiment needs. Thus, the influence of initial sorbent moisture, herbicide form, i.e. active substance or commercial formulation, water quality (tap or natural ditch water), bromide ions (used as conservative tracers) and solid/liquid ratio have been tested. Within the parameters investigated, pesticide formulation and solid/liquid ratio were the most important parameters affecting pesticide sorption on both ditch materials.     

Study of metabolites from the degradation of polycyclic aromatic hydrocarbons (PAHs) by bacterial consortium enriched from mangrove sediments

The PAH metabolites produced during degradation of fluorene, phenanthrene and pyrene by a bacterial consortium enriched from mangrove sediments were analyzed using the on-fiber silylation solid-phase microextraction (SPME) combining with gas chromatography–mass spectrometry (GC–MS) method. Seventeen metabolites at trace levels were identified in different PAH degradation cultures based on the full scan mass spectra. In fluorene degradation cultures, 1-, 2-, 3- and 9-hydroxyfluorene, fluorenone, and phthalic acid were detected. In phenanthrene and pyrene degradation cultures, various common metabolites such as phenanthrene and pyrene dihydrodiols, mono-hydroxy phenanthrene, dihydroxy pyrene, lactone and 4-hydroxyphenanthrene, methyl ester, and phthalic acid were found. The detection of various common and novel metabolites demonstrates that SPME combining with GC–MS is a quick and convenient method for identification as well as monitoring the real time changes of metabolite concentrations throughout the degradation processes. The knowledge of PAH metabolic pathways and kinetics within indigenous bacterial consortium enriched from mangrove sediments contributes to enhance the bioremediation efficiency of PAH in real environment.     

Broad range analysis of endocrine disruptors and pharmaceuticals using gas chromatography and liquid chromatography tandem mass spectrometry

Endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) have been globally detected in impacted natural waters. The detection of trace quantities of EDCs and PPCPs in the environment is of great concern since some of these compounds have known physiological responses at low concentrations. EDCs can have a wide range of polarities, acidic and basic moieties, and exist in trace quantities, which often requires numerous complex extractions, large sample collection volumes, and multiple instrumental analyses. A comprehensive method has been developed allowing for the analysis of 58 potential EDCs in various water matrices using a single solid-phase extraction (SPE) of a 1 L sample with subsequent analyses using both gas chromatography and liquid chromatography, each coupled with tandem mass spectrometry (GC–MS/MS and LC–MS/MS). Instrument detection limits ranged between 0.12–7.5 pg with corresponding method reporting limits of 1–10 ng l⁻¹ in water. Recoveries for most compounds were between 50% and 112% with good reproducibility (RSD 6–22%).