Characterisation of brown coal humic acids and modified humic acids using pyrolysis gcms and other techniques

It has been proposed that Victorian brown coal can be considered as a two-component structure — a lignocellulosic “host”, containing various amounts of weakly bound or entrapped “guest” material together with very small amounts of inorganic and/or mineral matter. The latter predominantly consists of wax esters and/or terpenoid material. In this paper we describe attempts to gain structural information regarding the more complex, “host” component of the coal. Our initial model compound has been humic acid that can be readily obtained from the coal by alkaline extraction. It has been found that “pure” humic acid, free from material associated with the “guest” components of the coal, can be obtained by a highly selective, low-yielding alkaline extraction. This humic acid has been studied by nmr spectroscopy and pyrolysis gas chromatography-mass spectroscopy (py-gc/ms). The products arising from py-gc/ms have been compared with those obtained from similar pyrolysis of whole coals. Alkylation of humic acids using alkyl halides in the presence of base has been successfully carried out and reactivity of the resulting materials compared with those of the parent coal and humic acid.     

Temporal variation in the arsenic and metal accumulation in the maritime pine tree grown on contaminated soils

The uptake of arsenic and other metals (iron, manganese, copper, zinc, lead, nickel and tungsten) by Pinus pinaster Aiton (the maritime pine tree) growing in soils and tailings around an abandoned mine (northern Portugal) was investigated. Aerial parts of Pinus pinaster trees were sampled from three substrate areas: a background area, in mine contaminated soils and in tailings. Vegetation material was separated into needles and stems and subdivided into tissues of different maturities (1-, 2-, 3- and 4-years-old). The sampling of the substrate in each area was also undertaken. In general, vegetation concentrations were strongly related to substrate concentrations. The results show that the contents of several elements depend as much on the plant organ as on the age of the tissue. For the researched elements, this species shows a great variability in behavior depending on the age of the organ. The data indicate that the older needles constitute the best samples for use in a conjunct biogeochemical analysis of these elements.     

Hydrochemistry of superficial waters in the Adoria mine area (Northern Portugal): environmental implications

The purpose of this work is to characterize the hydrochemical behavior of acid mine drainages (AMD) and superficial waters from the Adoria mine area (Northern Portugal). Samples of superficial and mine drainage water were collected for one year, bi-monthly, with pH, temperature, Eh, conductivity and HCO₃ determined in situ with chemical analyses of SO₄, Ca, K, Mg, Na, Cl, Ag, As, Bi, Co, Cu, Fe, Mn, Ni, Pb, Zn and Cd. In the mine, there are acidic waters, with low pH and significant concentrations of SO₄, and metals (Fe, Mn, Zn, Cu, Pb, Cd and Ni), while in the superficial natural stream waters outside the mine, the pH is close to neutral, with low conductivity and lower metal concentrations. The stream waters inside the mine influence are intermediate in composition between AMD and natural stream waters outside the mine influence. Principal Component Analysis (PCA) shows a clear separation between AMD galleries and AMD tailings, with tailings having a greater level of contamination.     

Selective chemical extraction of heavy metals in tailings and soils contaminated by mining activity: Environmental implications

Total concentrations of chemical elements in soils may not be enough to understand the mobility and bioavailability of the elements. It is important to characterise the degree of association of chemical elements in different physical and chemical phases of soil. Another geochemical characterisation methodology is to apply sequential selective chemical extraction techniques. A seven-step sequential extraction procedure was used to investigate the mobility and retention behaviour of Al, Fe, Mn, Cu, Zn, Pb, Cr, Co, Ni, Mo, Cd, Bi, Sn, W, Ag, As and U in specific physical–chemical and mineral phases in mine tailings and soils in the surroundings of the abandoned Ervedosa mine. The soil geochemical data show anomalies associated with mineralised veins or influenced by mining. Beyond the tailings, the highest recorded concentrations for most elements are in soils situated in mineralised areas or under the influence of tailings. The application of principal components analysis allowed recognition of (a) element associations according to their geochemical behaviour and (b) distinction between samples representing local geochemical background and samples representing contamination. Some metal cations (Mn, Cd, Cu, Zn, Co, Cr, Ni) showed important enrichment in the most mobilisable and bioavailable (i.e., water-soluble and exchangeable) fractions due likely to the acidic conditions in the area. In contrast, oxy-anions such as Mo and As showed lower mobility because of adsorption to Fe oxy-hydroxides. The residual fraction comprised largest proportions of Sn and Al and to a lesser extent Zn, Pb, Ni, Cr, Bi, W, and Ag, which are also present at low concentrations in the bioavailable fractions. The elements in secondary mineral phases (mainly Fe, Mn, Cu, Zn, Cd, Pb, W, Bi, Mo, Cr, Ni, Co, As and U) as well as in organic matter and sulphides are temporarily withheld, suggesting that they may be released to the environment by changes in physico-chemical conditions.