Organic-geochemical Differentiation of Petroleum-type Pollutants and Study of Their Fate in Danube Alluvial Sediments and Corresponding Water (Pančevo Oil Refinery, Serbia)

A review is given in this paper of the up-to-date results observed in differentiation and transformation studies on petroleum-type pollutants in underground and surface waters. Water and particulate matter derived from the locality of Pan?evo Petroleum Refinery, Serbia (River Danube alluvial formations). It was shown that distributions of n-alkanes, steranes and triterpanes, and δ¹³C_PDB values of n-alkanes may successfully be used for qualitatively differentiating the petroleum-type pollutants from native organic matter in recent sedimentary formations. In underground waters, a petroleum-type pollutant is exposed to microbiological degradation which is manifested through relatively fast degradation of n-alkanes. Following an almost complete degradation of crude oil n-alkanes in underground water, the biosynthesis of novel, even carbon-number C₁₆–C₃₀ n-alkanes may be observed. It is shown that the n-alkane distribution observed in a petroleum-type pollutant may depend on the intensity of its previous interaction with water. The fate of petroleum-type pollutants in environmental waters may be predicted through laboratory simulative microbiological degradation experiments by using microorganism consortiums similar to those observed under relevant natural conditions, as well as on corresponding nutrient base.     

Spatial and vertical distribution of <Superscript>137</Superscript>Cs in soils in the erosive area of southeastern Serbia (Pčinja and South Morava River Basins)

Purpose

The area of southeastern Serbia, the P?inja and South Morava River Basins, is under the influence of very strong erosion, and the aim of this study was to investigate the vertical and spatial distribution of the ¹³⁷Cs in the eroded soils of this area.

Materials and methods

Vertical soil profiles were collected with 5-cm increments from the uppermost layer down to 20, 25, 30, 40, and 50 cm of depth, depending on the thickness of the soil layers, i.e., down to the underlying parent rocks. Measurements of ¹³⁷Cs activity concentration were performed by using the HPGe gamma-ray spectrometer ORTEC-AMETEK (34 % relative efficiency and high resolution 1.65 keV at 1.33 MeV for ⁶⁰Co), from its gamma-ray line at 661.2 keV.

Results and discussion

The mean ¹³⁷Cs activity concentration across all 18 soil profiles (for all soil layers) was found to be 20 Bq kg^?1. In the greatest number of soil profiles, the ¹³⁷Cs activity concentration was generally highest in the first soil layer (0–5 cm) and decreased with soil depth, while in a few soil profiles, the peak of either the ¹³⁷Cs activity concentration occurred in the second soil layer (5–10 cm) or the ¹³⁷Cs activity concentration was almost equal throughout the entire soil profile. The mean ¹³⁷Cs activity concentration in the first soil layer (0–5 cm) was found to be 61 Bq kg^?1, and the high coefficient of variation of 92 % pointed out high spatial variability and large range of the ¹³⁷Cs activity concentrations in the study area.

Conclusions

The obtained results indicate that in the greatest number of soil profiles, ¹³⁷Cs is present in the upper layers, with concentration decreasing with depth, as is typical in uncultivated soil. Its spatial distribution was very uneven among the surface soil layers of the investigated sites. One of the main reasons for such pattern of ¹³⁷Cs in the study area may be soil erosion. Additional investigations which would support this hypothesis are required.

     

Effects of root exudates and humic substances on weathering kinetics

The effect of complex natural organic ligands on the weathering kinetics of aluminum oxide was investigated in laboratory experiments. A peat-derived humic substance and root exudates obtained from ectomycorrhizal (Picea abies — Hebeloma crustuliniforme) and non-mycorrhizal Norway Spruce trees; and γ-Al₂O₃ were used as a model system. The experimental weathering rates are in accordance with a surface-controlled dissolution mechanism. The effect of the humic material on dissolution rates appears to depend on the degree of protonation of the humic (macro)molecules: we observed dissolution-enhancement or -inhibition at pH 3 and 4, respectively. Ectomycorrhizal exudates proved to be effective weathering agents at pH 4, as opposed to humic material and non-mycorrhizal exudates. Our results suggest that (i) the role of humic materials in mineral weathering and podzolization is different from what is commonly thought, and (ii) mineral weathering rates in the rhizosphere may be higher than in the bulk soil.     

Principal component analysis of trace elements in Serbian wheat

Trace elements (Cu, Fe, Pb, Hg, Cd, As, Mn, Zn) were analyzed quantitatively in 14 wheat samples collected from fields in all Serbian growing regions, harvested in 2002. Microelements were determined according to an atomic absorption spectrophotometric method. Principal component analyses (PCA) were performed on data matrices consisting of contents of trace elements in wheats (columns) and all Serbian wheat-growing regions (rows). It was found that four principal components account for 87.2% of the total variance in the data. The plot of component loadings showed significant groupings for concentration of some microelements. The component scores indicated the similarities among the Serbian wheat-growing regions. The loading plot reveals that there is no need to measure all of the variables to achieve the same classification. It is enough to measure one variable per group. Naturally, this conclusion is valid only within the limits of the present study of wheat grain samples from different parts of Serbia.     

Use of the BCR three-step sequential extraction procedure for the study of the partitioning of Cd, Pb and Zn in various soil samples

A slightly modified three-step sequential extraction procedure proposed by the Community Bureau of Reference (BCR) for analysis of sediments was successfully applied to soil samples. Contaminated soil samples from the lead and zinc mining area in the Mezica valley (Slovenia) and natural soils from a non-industrial area were analysed. The total concentrations of Cd, Pb and Zn and their concentrations in fractions after extraction were determined by flame or electrothermal atomic absorption spectrometry (FAAS, ETAAS). Total metal concentrations in natural soils ranged from 0.3 to 2.6 mg kg^-1 for Cd, from 20 to 45 mg kg^-1 for Pb and from 70 to 140 mg kg^-1 for Zn, while these concentrations ranged from 0.5 to 35 mg kg^-1 for Cd, from 200 to 10000 mg kg^-1 for Pb and from 140 to 1500 mg kg^-1 for Zn in soils from contaminated areas. The results of the partitioning study applying the slightly modified BCR three-step extraction procedure indicate that Cd, Pb and Zn in natural soils prevails mostly in sparingly soluble fractions. Cd in natural soils is bound mainly to Fe and Mn oxides and hydroxides, Pb to organic matter, sulphides and silicates, while Zn is predominantly bound to silicates. In contaminated soils, Cd, Pb and Zn are distributed between the easily and sparingly soluble fractions. Due to the high total Cd, Pb and Zn concentrations in contaminated soil close to the smelter, ! and their high proportions in the easily soluble fraction (80% of Cd, 50% of Pb and 70% of Zn), the soil around smelters represents an environmental hazard.     

Determination of Plant-Available Nutrients in Two Wood Ashes: The Influence of Combustion Conditions

Wood ashes were traditionally used as a fertilizing agent from the very beginning of working land but the fertilizing quality varies according to the combusted biomass and also the industrial burning equipment. The differences between wood ash originated from fluid and classic boiler were investigated by X-ray powder diffraction (XRD), X-ray fluorescence spectrometry (XRF), differential thermal analysis (DTA), thermo-gravimetric analysis (TGA), scanning electron microscopy (SEM), and Mehlich 3 and deionized water extraction procedures in relation to extraction time. The results, especially of the SEM and chemical extractions, have demonstrated that the type of burning boiler determines the portions of the leachable nutrient elements. The silica and alumina ash content conducted by the elevated temperature transforms the main proportion of calcium and potassium into the insoluble feldspars. Due to this effect only a small amount of nutrients could be released and served as a fertilizing matter.     

Assessment of soil organic matter mineralization under various management practices

ABSTRACT

Mineralization is the main organic matter conversion process, which leads not only to preservation of organic matter in the soil but also to its sequestration. Soil organic matter has equal value as mineral part if we want to improve soil quality or increase the yield. Because of intensive farming, irresponsible use of mineral fertilizers and natural factors, soil organic matter is decreasing. To counteract this process, different soil-friendly management practices and techniques, such as shallow tillage, no-tillage or direct drilling and application of additional organic matter are used. The objective of the present study was to assess the changes in the intensity of soil organic matter mineralization as influenced by primary soil tillage of different intensity in combination with organic matter incorporation. Long-term studies showed that land management practices differentiated the soil into two layers: upper (0–10?cm) layer containing more moisture and nutrients and lower (10–20?cm) layer comprising less moisture and nutrients. The conditions of aeration in the arable soil layer did not change under the effect of ploughing. In this soil, the rate of mineralization was lower than that in the ploughless tillage treatment. The most active mineralization of soil organic matter in the ploughless tillage treatment occurred in the autumn period, when high level of rainfall promoted the loss of nutrients from the topsoil layer.     

Macroinvertebrate Community and Chemistry of the Most Atmospherically Acidified Streams in the Czech Republic

We performed a comparative study of strongly acidified mountain streams covering 10 sites in the Czech Republic in the season 1999/2000. The aim of the study was to determine how acidification influenced macroinvertebrate community structure within a relatively narrow pH range. We focused on strongly acidified, non-humic running waters with low ionic content (pH < 4.6, total organic carbon < 10 mg l^?1, specific conductivity < 100 μS cm^?1) and minimum human influence in the catchment. The actual pH values ranged from 3.98 to 4.65, and concentrations of reactive aluminium ranged from 0.2 to 2.0 mg l^?1. Characteristic macroinvertebrates were the stoneflies Leuctra nigra, Nemurella pictetii, and Protonemura spp.; the chironomids Corynoneura spp.; and the caddisfly Plectrocnemia conspersa – the former two stoneflies formed together 46% of total organisms. The sites were divided into three groups with use of divisive classification. Individual groups reflected similarity in water chemistry, catchment characteristics, and geographical proximity. The largest biotic difference detected by PCA was in the abundance of stoneflies, mainly Diura bicaudata and Leuctra major. The strongest correlation with this gradient was shown by pH (and associated heavy metals), followed by the distance from source. The results show that even in such narrow pH range, the number of taxa is determined by the low pH value and related high concentrations of aluminium and heavy metals.     

Influence of grain type on the insecticidal efficacy of two diatomaceous earth formulations against Rhyzopertha dominica (F) (Coleoptera: Bostrychidae)

Laboratory bioassays were carried out in order to evaluate the effectiveness of two diatomaceous earth (DE) formulations, Insecto and SilicoSec, against adults of Rhyzopertha dominica (F) in eight different grain commodities. The adherence of the two DEs to each grain was also measured. The eight grains tested were wheat, whole barley, peeled barley, oats, rye, triticale, rice and maize. These commodities were treated with the DEs at three rates, 0.75, 1.0 and 1.5 g DE kg(-1) grain. The mortality of R dominica adults was measured after 24 h, 48 h, 7 days and 14 days of exposure in the treated grains at 26 degrees C and 55% RH. After the 14-day mortality count, all adults were removed and the treated grains retained under the same conditions for a further 60 days. The treated grains were subsequently examined for F1 progeny. Significant differences were recorded among the eight grain types as well as between the DE formulations tested. After 14 days of exposure, even at the lowest DE rate for both formulations, adult mortality was high (>90%) in wheat and triticale. In contrast, adult mortality was significantly lower in peeled barley. Increasing the rate improved the efficacy of the DEs significantly in only some of the grains tested. Reproductive capacity in all the treated grains was significantly suppressed when compared with untreated grains. Generally, more F1 individuals of R dominica were noted in the treated peeled barley than in the other commodities. Significant differences in the percentage of DE retention were noted among the eight grains. The highest retention level was noted in rice (>87%) and the lowest in maize (<6%). However, the degree of DE adherence to a given grain was not always indicative of the effectiveness of DE against R dominica.     

Correlation of Different Biochemical Parameters in Blood Sera of Healthy and Sick Cows

Metabolic diseases of cows represent the leading internal pathology in Lithuania in terms of incidence and economic impact. This paper summarizes the mineral metabolic state of milk cows, and details the influence of feeding on serum levels of calcium, nonorganic phosphorus, magnesium, potassium, sodium, glucose, total protein, and urea quantity, and correlationd among them, in healthy dry or post-calving cows as well as in cows with osteomalacia and milk fever after calving. There was less pronounced hypocalcaemia and there were only minor changes in phosphorus, magnesium, potassium and sodium in the serum of healthy dry and post-calving cows that had silage and mineral-vitamin supplements, compared to cows that did not have supplements and silage. There was a fall in calcium and phosphorus (to 1.89 +/- 0.12 mmol/L and 0.71 +/- 0.06 mmol/L, respectively) in the blood of cows sick with milk fever after calving, while levels of magnesium and potassium were increased. The correlation between calcium and phosphorus was r = 0.6993, p < 0.001 in the serum of sick cows. There was a fall in calcium, phosphorus and magnesium (to 1.86 +/- 0.46 mmol/L, 0.75 +/- 0.37 mmol/L, and 0.60 +/- 0.19 mmol/L, respectively) and an increase in sodium level (to 158.90 +/- 19.30 mmol/L) in the blood of cows with osteomalacia in comparison with healthy cows.