Partitioning of metals in a degraded acid sulfate soil landscape: influence of tidal re-inundation

The oxidation and acidification of sulfidic soil materials results in the re-partitioning of metals, generally to more mobile forms. In this study, we examine the partitioning of Fe, Cr, Cu, Mn, Ni and Zn in the acidified surface soil (0-0.1 m) and the unoxidised sub-soil materials (1.3-1.5 m) of an acid sulfate soil landscape. Metal partitioning at this acidic site was then compared to an adjacent site that was previously acidified, but has since been remediated by tidal re-inundation. Differences in metal partitioning were determined using an optimised six-step sequential extraction procedure which targets the “labile”, “acid-soluble”, “organic”, “crystalline oxide”, “pyritic” and “residual” fractions. The surficial soil materials of the acidic site had experienced considerable losses of Cr, Cu, Mn and Ni compared to the underlying parent material due to oxidation and acidification, yet only minor losses of Fe and Zn. In general, the metals most depleted from the acidified surface soil materials exhibited the greatest sequestration in the surface soil materials of the tidally remediated site. An exception to this was iron, which accumulated to highly elevated concentrations in the surficial soil materials of the tidally remediated site. The “acid-soluble”, “organic” and “pyritic” fractions displayed the greatest increase in metals following tidal remediation. This study demonstrates that prolonged tidal re-inundation of severely acidified acid sulfate soil landscapes leads to the immobilisation of trace metals through the surficial accumulation of iron oxides, organic material and pyrite.     

Marine and farmed fish on the Polish market: comparison of the nutritive value and human exposure to PCDD/Fs and other contaminants

Chemical analyses were performed in nine fish species that are popular on the Polish market. These included Baltic fish (cod, herring, salmon), fish farmed in Poland (carp, trout), marine fish imported from China (Alaska pollock, sole), and farmed fish imported from Vietnam and China (sutchi catfish, tilapia). The nutritional composition (amino acid, micro- and macronutrients, fat-soluble vitamins - A₁, D₃, E) and certain contaminants (organochlorine pesticides, OCPs; indicator polychlorinated biphenyl, PCB₆; polychlorinated dibenzo-paradioxins and polychlorinated dibenzofurans, PCDD/Fs; dioxin-like polychlorinated biphenyls, dl-PCBs; organotin compounds, OCTs; dyes, malachite green and crystal violet; veterinary drug residues, nitrofurans and chloramphenicol; toxic metals, Cd, Pb, Hg) in the muscle tissues of fish were determined. It was confirmed that the fish species analyzed were excellent sources of amino acids, and were rich in phosphorous and selenium. Baltic Sea fish (salmon, herring), fish farmed in Poland (carp and trout), and tilapia were also rich in vitamin D₃.Traces of OCP, PCB₆, OCT, dyes, veterinary drug residues, and heavy metals were detected in concentrations which do not pose a threat to consumers at the current rate of fish consumption in Poland. However, the problem might arise from the content of PCDD/Fs and dl-PCBs in fatty Baltic fish. The fish species analyzed, differed in their nutritional values and degrees of contamination. We suggest that for optimum health and safety, it is advisable that consumers include a variety of different fish species in their diets.     

Fate of nitrogen for subsurface drip dispersal of effluent from small wastewater systems

Subsurface drip irrigation systems apply effluent from onsite wastewater systems in a more uniform manner at a lower rate than has been possible with other effluent dispersal methods. The effluent is dispersed in a biologically active part of the soil profile for optimal treatment and where the water and nutrients can be utilized by landscape plants. Container tests were performed to determine the fate of water and nitrogen compounds applied to packed loamy sand, sandy loam, and silt loam soils. Nitrogen removal rates measured in the container tests ranged from 63 to 95% despite relatively low levels of available carbon. A Hydrus 2D vadose zone model with nitrification and denitrification rate coefficients calculated as a function of soil moisture content fit the container test results reasonably well. Model results were sensitive to the denitrification rate moisture content function. Two-phase transport parameters were needed to model the preferential flow conditions in the finer soils. Applying the model to generic soil types, the greatest nitrogen losses (30 to 70%) were predicted for medium to fine texture soils and soils with restrictive layers or capillary breaks. The slow transport with subsurface drip irrigation enhanced total nitrogen losses and plant nitrogen uptake opportunity.     

Transport of Escherichia coli in 25 m quartz sand columns

To help improve the prediction of bacteria travel distances in aquifers laboratory experiments were conducted to measure the distant dependent sticking efficiencies of two low attaching Escherichia coli strains (UCFL-94 and UCFL-131). The experimental set up consisted of a 25 m long helical column with a diameter of 3.2 cm packed with 99.1% pure-quartz sand saturated with a solution of magnesium sulfate and calcium chloride. Bacteria mass breakthrough at sampling distances ranging from 6 to 25.65 m were observed to quantify bacteria attachment over total transport distances (α(L)) and sticking efficiencies at large intra-column segments (α(i)) (>5m). Fractions of cells retained (F(i)) in a column segment as a function of α(i) were fitted with a power-law distribution from which the minimum sticking efficiency defined as the sticking efficiency of 0.001% bacteria fraction of the total input mass retained that results in a 5 log removal were extrapolated. Low values of α(L) in the order 10(-4) and 10(-3) were obtained for UCFL-94 and UCFL-131 respectively, while α(i)-values ranged between 10(-6) to 10(-3) for UCFL-94 and 10(-5) to 10(-4) for UCFL-131. In addition, both α(L) and α(i) reduced with increasing transport distance, and high coefficients of determination (0.99) were obtained for power-law distributions ofα(i) for the two strains. Minimum sticking efficiencies extrapolated were 10(-7) and 10(-8) for UCFL-94 and UCFL-131, respectively. Fractions of cells exiting the column were 0.19 and 0.87 for UCFL-94 and UCL-131, respectively. We concluded that environmentally realistic sticking efficiency values in the order of 10(-4) and 10(-3) and much lower sticking efficiencies in the order 10(-5) are measurable in the laboratory, Also power-law distributions in sticking efficiencies commonly observed for limited intra-column distances (<2m) are applicable at large transport distances(>6m) in columns packed with quartz grains. High fractions of bacteria populations may possess the so-called minimum sticking efficiency, thus expressing their ability to be transported over distances longer than what might be predicted using measured sticking efficiencies from experiments with both short (<1m) and long columns (>25 m). Also variable values of sticking efficiencies within and among the strains show heterogeneities possibly due to variations in cell surface characteristics of the strains. The low sticking efficiency values measured express the importance of the long columns used in the experiments and the lower values of extrapolated minimum sticking efficiencies makes the method a valuable tool in delineating protection areas in real-world scenarios.     

Body metal concentrations and glycogen reserves in earthworms (Dendrobaena octaedra) from contaminated and uncontaminated forest soil

Stress originating from toxicants such as heavy metals can induce compensatory changes in the energy metabolism of organisms due to increased energy expenses associated with detoxification and excretion processes. These energy expenses may be reflected in the available energy reserves such as glycogen. In a field study the earthworm, Dendrobaena octaedra, was collected from polluted areas, and from unpolluted reference areas. If present in the environment, cadmium, lead and copper accumulated to high concentrations in D. octaedra. In contrast, other toxic metals such as aluminium, nickel and zinc appeared to be regulated and kept at low internal concentrations compared to soil concentrations. Lead, cadmium and copper accumulation did not correlate with glycogen reserves of individual worms. In contrast, aluminium, nickel and zinc were negatively correlated with glycogen reserves. These results suggest that coping with different metals in earthworms is associated with differential energy demands depending on the associated detoxification strategy.     

The impact of nitrogen deposition on acid grasslands in the Atlantic region of Europe

A survey of 153 acid grasslands from the Atlantic biogeographic region of Europe indicates that chronic nitrogen deposition is changing plant species composition and soil and plant-tissue chemistry. Across the deposition gradient (2-44 kg N ha⁻¹ yr⁻¹) grass richness as a proportion of total species richness increased whereas forb richness decreased. Soil C:N ratio increased, but soil extractable nitrate and ammonium concentrations did not show any relationship with nitrogen deposition. The above-ground tissue nitrogen contents of three plant species were examined: Agrostis capillaris (grass), Galium saxatile (forb) and Rhytidiadelphus squarrosus (bryophyte). The tissue nitrogen content of neither vascular plant species showed any relationship with nitrogen deposition, but there was a weak positive relationship between R. squarrosus nitrogen content and nitrogen deposition. None of the species showed strong relationships between above-ground tissue N:P or C:N and nitrogen deposition, indicating that they are not good indicators of deposition rate.     

Evolution of organic matter during composting of different organic wastes assessed by CPMAS 13C NMR spectroscopy

In this paper, the evolution of organic matter (OM) during composting of different mixtures of various organic wastes was assessed by means of chemical analyses and CPMAS ¹³C NMR spectroscopy measured during composting. The trends of temperatures and C/N ratios supported the correct evolution of the processes. The CPMAS ¹³C NMR spectra of all composting substrates indicated a reduction in carbohydrates and an increase in aromatic, phenolic, carboxylic and carbonylic C which suggested a preference by microorganisms for easily degradable C molecules. The presence of hardly degradable pine needles in one of the substrates accounted for the lowest increase in alkyl C and the lowest reduction in carbohydrates and carboxyl C as opposite to another substrate characterized by the presence of a highly degradable material such as spent yeast from beer production, which showed the highest increase of the alkyl C/O-alkyl C ratio. The highest increase of COOH deriving by the oxidative degradation of cellulose was shown by a substrate composed by about 50% of plant residues. The smallest increases in alkyl C/O-alkyl C ratio and in polysaccharides were associated to the degradation of proteins and lipids which are major components of sewage sludge. Results obtained were related to the different composition of fresh organic substrates and provided evidence of different OM evolution patterns as a function of the initial substrate composition.     

An ecotoxicological approach for hazard identification of energy ash

Within the EU, ash should be classified by its inherent hazardous effects under criterion H-14 (ecotoxic) in the Directive on waste (2008/98/EC). Today, however, there are no harmonized quantitative criterions for such a classification, but it is stated that biological test systems can be used. In this study seven ash materials were leached and characterized, both biologically and chemically. The objectives were to evaluate if (a) clear concentration-response relationships could be achieved for the selected toxicity tests (bacteria, algae, crustacean and fish), (b) some test(s) are generally more sensitive and (c) the toxic responses were consistent with the chemical analyzes. Interestingly, our results indicate that high concentrations of non-hazardous components (Ca, K) influenced the toxicity of almost all ash eluates, whereas hazardous components (e.g. Zn, Pb) only influenced the toxicity of the eluates ranked as most hazardous. If considering both hazardous and non-hazardous substances, the observed toxic responses were relatively consistent with the chemical analyzes. Our results further showed that the (sub)chronic tests were much more sensitive than the acute tests. However, the use of extrapolation factors to compensate for using the less sensitive acute tests will likely lead to either over- or underestimations of toxicity. Our recommendation is therefore that classification of waste according to H-14 should be based on (sub)chronic test data. Finally, given that treatment of the eluates prior to toxicity testing has a major significance on the concentration and speciation of released substances, further studies are needed in order to propose a relevant testing scheme.     

Impact of different plants on the gas profile of a landfill cover

Methane is an important greenhouse gas emitted from landfill sites and old waste dumps. Biological methane oxidation in landfill covers can help to reduce methane emissions. To determine the influence of different plant covers on this oxidation in a compost layer, we conducted a lysimeter study. We compared the effect of four different plant covers (grass, alfalfa + grass, miscanthus and black poplar) and of bare soil on the concentration of methane, carbon dioxide and oxygen in lysimeters filled with compost. Plants were essential for a sustainable reduction in methane concentrations, whereas in bare soil, methane oxidation declined already after 6 weeks. Enhanced microbial activity - expected in lysimeters with plants that were exposed to landfill gas - was supported by the increased temperature of the gas in the substrate and the higher methane oxidation potential. At the end of the first experimental year and from mid-April of the second experimental year, the methane concentration was most strongly reduced in the lysimeters containing alfalfa + grass, followed by poplar, miscanthus and grass. The observed differences probably reflect the different root morphology of the investigated plants, which influences oxygen transport to deeper compost layers and regulates the water content.