Variation of MCPA, metribuzine, methyltriazine-amine and glyphosate degradation, sorption, mineralization and leaching in different soil horizons

Pesticide mineralization and sorption were determined in 75 soil samples from 15 individually drilled holes through the vadose zone along a 28 km long transect of the Danish outwash plain. Mineralization of the phenoxyacetic acid herbicide MCPA was high both in topsoils and in most subsoils, while metribuzine and methyltriazine-amine was always low. Organic matter and soil pH was shown to be responsible for sorption of MCPA and metribuzine in the topsoils. The sorption of methyltriazine-amine in topsoil was positively correlated with clay and negatively correlated with the pH of the soil. Sorption of glyphosate was tested also high in the subsoils. One-dimensional MACRO modeling of the concentration of MCPA, metribuzine and methyltriazine-amine at 2 m depth calculated that the average concentration of MCPA and methyltriazine-amine in the groundwater was below the administrative limit of 0.1 μg/l in all tested profiles while metribuzine always exceeded the 0.1 μg/l threshold value.     

Levels of perfluorochemicals in water samples from Catalonia,Spain: is drinking water a significant contribution to human exposure?

Background, aim, and scope  In recent years, due to a high persistence, biomagnification in food webs, presence in remote regions, and potential toxicity, perfluorochemicals (PFCs) have generated a considerable interest. The present study was aimed to determine the levels of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and other PFCs in drinking water (tap and bottled) and river water samples from Tarragona Province (Catalonia, Spain). Materials and methods  Municipal drinking (tap) water samples were collected from the four most populated towns in the Tarragona Province, whereas samples of bottled waters were purchased from supermarkets. River water samples were collected from the Ebro (two samples), Cortiella, and Francolí Rivers. After pretreatment, PFC analyses were performed by HPLC-MS. Quantification was done using the internal standard method, with recoveries between 68% and 118%. Results  In tap water, PFOS and PFOA levels ranged between 0.39 and 0.87 ng/L (0.78 and 1.74 pmol/L) and between 0.32 and 6.28 ng/L (0.77 and 15.2 pmol/L), respectively. PFHpA, PFHxS, and PFNA were also other detected PFCs. PFC levels were notably lower in bottled water, where PFOS could not be detected in any sample. Moreover, PFHpA, PFHxS, PFOA, PFNA, PFOS, PFOSA, and PFDA could be detected in the river water samples. PFOS and PFOA concentrations were between <0.24 and 5.88 ng/L (<0.48 and 11.8 pmol/L) and between <0.22 and 24.9 ng/L (<0.53 and 60.1 pmol/L), respectively. Discussion  Assuming a human water consumption of 2 L per day, the daily intake of PFOS and PFOA by the population of the area under evaluation was calculated (0.78–1.74 and 12.6 ng, respectively). It was found that drinking water might be a source of exposure to PFCs as important as the dietary intake of these pollutants. Conclusions  The contribution of drinking water (tap and bottled) to the human daily intake of various PFCs has been compared for the first time with data from dietary intake of these PFCs. It was noted that in certain cases, drinking water can be a source of exposure to PFCs as important as the dietary intake of these pollutants although the current concentrations were similar or lower than those reported in the literature for surface water samples from a number of regions and countries. Recommendations and perspectives  Further studies should be carried out in order to increase the knowledge of the role of drinking water in human exposure to PFCs.     

Comparative effects of mine wastes on the benthos of an acid and an alkaline pond

Benthic invertebrates collected from an acid (pH 3.2) and an alkaline (pH 7.9) tailing pond in the Rouyn-Noranda mining region were compared with those of a control pond in order to assess the effects of the pH on the benthic community structure and on metal accumulation by invertebrates. The acid pond showed high mean soluble concentrations of aluminium (2600 ppb), copper (230 ppb), iron (6500 ppb) and zinc (4900 ppb) in the water and high mean concentrations of copper (340 ppm), iron (15,238 ppm) and zinc (445 ppm) in the sediments. The benthic fauna was dominated by Chironomus spp and the water beetle Ilybius sp. The Shannon-Weaver diversity index was 0.04. The alkaline pond had high mean sediment concentrations of cadmium (21 ppm), iron (15,823 ppm), manganese (658 ppm) and nickel (146 ppm). A total of 37 insect genera and a diversity index of 3.4 were recorded for this pond. Of the seven metals studied only copper and aluminium showed greater accumulations in the biota of the contaminated ponds than in that of the control. Insects dominated the benthic fauna in both contaminated ponds and crustacea in the control.     

Degradation of ethinyl estradiol by nitrifying activated sludge

Degradation of ethinyl estradiol (EE2) by nitrifying activated sludge was studied with micro-organisms grown in a reactor with feedback of sludge fed with only a mineral salts medium containing ammonium as the sole energy source. Ammonium was oxidised by this sludge at a rate of 50 mg NH4+ g(-1) DW h(-1). This activated sludge was also capable of degrading EE2 at a maximum rate of 1 microg g(-1) DW h(-1). Using sludge with an insignificant nitrifying capacity of 1 mg NH4+ g(-1) DW h(-1), no degradation of EE2 was detected. Oxidation of EE2 by nitrifying sludge resulted in the formation of hydrophilic compounds, which were not further identified. Most probably degradation by nitrifying sludge results in a loss of estrogenic activity, as hydroxylated derivatives of EE2 are known to have a substantially lower pharmacological activity than EE2.     

Persistent organochlorine compounds in soils and sediments of European high altitude mountain lakes

The composition of persistent organochlorine compounds (OC) in soils and sediments from two high altitude European mountain lakes, Redon in the Pyrenees and Ladove in the Tatra mountains, has been studied. Sediment cores from two additional lakes in the Tatra mountains, Starolesnianske Pleso and Dlugi Staw, have also been examined. DDTs (1.7-13 ng g(-1)) were the most abundant OC in soils followed by total polychlorobiphenyls (PCBs; 0.41-1.5 ng g(-1)) and hexachlorobenzene (HCB; 0.15-0.91 ng g(-1)). In sediments, the dominant OC were also DDTs (3.3-28 ng g(-1)) and PCBs (2.3-15 ng g(-1)). These concentrations are low, involving absence of major pollution sources in these high mountain regions. The downcore OC profiles in soils and sediments were similar but higher concentrations and steeper vertical gradients were observed in the latter. Radiometric determinations showed absence of significant OC transport from catchment to lake. The sediment-soil difference points therefore to a better retention of the OC load in sediments than soils which may be related to the low temperatures that are currently encountered at the bottom of the lake water column and the depletion of sediment bioturbation in these cold environments. Significant qualitative changes in the soil PCB distributions are observed downcore. These involve a dominance of the high molecular weight congeners in the top core sections and those of lower weight (i.e. less chlorinated) in the bottom. Anaerobic dechlorination of higher molecular weight congeners occurring in microsites, e.g. as observed in flooded or poorly drained soils, could be responsible for these changes. This process could be concurrent to bioturbation.     

Passive dosing: an approach to control mutagen exposure in the Ames fluctuation test

By using dialysis equilibrium experiments, the sorption of a branched nonylphenol isomer [4-(1-ethyl-1,3-dimethylpentyl)-phenol] (NP111) on various humic acids (HAs) isolated from river sediments and two reference HAs was studied. The HAs were characterized by solid-state ¹³C direct polarization/magic angle spinning nuclear magnetic resonance (¹³C DP/MAS NMR) spectroscopy. Sorption isotherms of NP111 on HAs were described by a linear model. The organic carbon-normalized sorption coefficient (K_OC) ranged from 2.3 × 10³ to 1.5 × 10⁴ L kg⁻¹. Interestingly, a clear correlation between K_OC value and alkyl C content was observed, indicating that the aliphaticity of HAs markedly dominates the sorption of NP111. These new mechanistic insights about the NP111 sorption indicate that the fate of nonylphenols in soil or sediment depends not only on the content of HA, but also on its structural composition.     

Effects of Acidification and its Mitigation with Lime and Wood Ash on Forest Soil Processes: A Review

Anthropogenic acid deposition causes forest soil acidification and perturbation of the soil forming processes. The impact of soil acidification on tree growth is discussed in view of the role of mycorrhizal fungi in weathering and nutrient uptake. A review has been carried out of experiments involving treatments of forest soil by lime and wood ash, where soil properties and soil solution composition have been investigated. Results from these experiments in Europe and North America are summarized. In general, the content of C in the mor layer decreased as a result of treatment due to higher microbial activity and soil respiration as well as increased leakage of DOC. In addition, the content of N in the mor layer, in general, decreased after treatment and there are occasional peaks of high NO₃concentrations in soil solution. In nearly all reviewed investigations the pH of the deep mineral soil solution decreased and Al, SO₄and NO₃concentrations increased after treatment. These effects are probably due to the high ionic strength and increased microbial activity as a consequence of the treatments. In the soil, pH, CEC and base saturation increased in the upper horizons, but decreases in the upper mineral soil are also reported. In general, there was no increase in tree growth as a result of these treatments. The positive effects of the treatments on soil processes and tree growth are therefore questionable. In view of these conclusions, an investigation was carried out on the soil and soil solution chemistry and the role of mycorrhizal fungi in a spruce stand treated with two doses of lime and another treated with lime/ash in southern Sweden. The results of this investigation is reported in this volume.     

Structure-biodegradation relationships of polymeric materials. 1. Effect of degree of oxidation on biodegradability of carbohydrate polymers

The biodegradability of oxidized starch and inulin has been studied in relation to the degree of periodate oxidation to dialdehyde derivatives, by measuring oxygen consumption and mineralization to carbon dioxide. A higher degree of oxidation of dialdehyde starch and dialdchyde inulin results in a lower rate at which the polymers are biodegraded. It is demonstrated that the biodegradation rate of dialdehyde inulin derivatives decreases more than that of equivalent starch derivatives. The differences in biodegradation behavior between dialdehyde starch and dialdehyde inulin, resulting from comparable modifications, are discussed in terms of conformational structure.     

Ecological impacts of early 21st century agricultural change in Europe – A review

The impacts of agricultural land use are far-reaching and extend to areas outside production. This paper provides an overview of the ecological status of agricultural systems across the European Union in the light of recent policy changes. It builds on the previous review of 2001 devoted to the impacts of agricultural intensification in Western Europe. The focus countries are the UK, The Netherlands, Boreal and Baltic countries, Portugal, Hungary and Romania, representing a geographical spread across Europe, but additional reference is made to other countries. Despite many adjustments to agricultural policy, intensification of production in some regions and concurrent abandonment in others remain the major threat to the ecology of agro-ecosystems impairing the state of soil, water and air and reducing biological diversity in agricultural landscapes. The impacts also extend to surrounding terrestrial and aquatic systems through water and aerial contamination and development of agricultural infrastructures (e.g. dams and irrigation channels). Improvements are also documented regionally, such as successful support of farmland species, and improved condition of watercourses and landscapes. This was attributed to agricultural policy targeted at the environment, improved environmental legislation, and new market opportunities. Research into ecosystem services associated with agriculture may provide further pressure to develop policy that is targeted at their continuous provisioning, fostering motivation of land managers to continue to protect and enhance them.     

European scale application of atmospheric reactive nitrogen measurements in a low-cost approach to infer dry deposition fluxes

A European scale network was established in 2006 as part of the NitroEurope Integrated Project to infer reactive nitrogen (Nr) dry deposition fluxes, based on low-cost sampling of gaseous and aerosol species and inferential modelling. The network provides monthly measurements of NH₃, NH₄⁺, HNO₃ and NO₃⁻, as well as SO₂, SO₄²⁻, HCl, Cl⁻ and base cations at 58 sites. Measurements are made with an established low-cost denuder methodology (DELTA) as a basis to: (1) examine temporal trends and spatial patterns across Europe, (2) improve and calibrate inferential modelling techniques to estimate exchange of Nr species, (3) provide best estimates of atmospheric dry N deposition, and (4) permit an analysis of net GHG exchange in relation to atmospheric and agricultural N inputs at the European scale. Responsibility for measurements is shared among seven European laboratories. An inter-comparison of the DELTA implementation by 6 laboratories at 4 test sites (Montelibretti, Italy; Braunschweig, Germany; Paterna, Spain and Auchencorth, UK) from July to October 2006 provided training for the laboratories and showed that good agreement was achieved in different climatic conditions (87% of laboratory site-means within 20% of the inter-laboratory median). Results obtained from the first year of measurements show substantial spatial variability in atmospheric Nr concentrations, illustrating the major local (NH₃) and regional (HNO₃, NO₃⁻, and NH₄⁺) differences in Nr concentrations. These results provide the basis to develop future estimates of site-based Nr dry deposition fluxes across Europe, and highlight the role of NH₃, largely of agricultural origin, which was the largest single constituent and will dominate dry Nr fluxes at most sites.