Assessment of pesticide inputs into surface waters by agricultural and urban sources - A case study in the Querne/Weida catchment, central Germany.

Pesticide inputs into surface waters may cause harmful effects on aquatic life communities and substantially contribute to environmental pollution. The present study aimed at evaluating the input pathways in the Querne/Weida catchment (central Germany) to efficiently target mitigation measures of pesticide losses. Relevant pesticide substances were measured in surface waters in agricultural and urban surroundings and in soil samples within the catchment area. Pesticides application data from farmers were analyzed. Additionally, batch tests were performed to determine sorption and degradation of relevant pesticides for site specific soil properties. Frequency of detection, number of pesticides and maximum concentrations were much higher in the surface water samples in mainly urban surroundings compared to those in agricultural surrounding. The most frequently detected substances were glyphosate, AMPA, diflufenican and tebuconazole in surface water samples and diflufenican, boscalid, tebuconazole and epoxiconazole in the topsoil samples. Glyphosate and AMPA contributed to the highest concentrations in surface water samples (max. 58 µg L-1) and soil samples (max. 0.19 mg kg-1). In most cases, pesticide detections in surface water and soil were not consistent with application data from farmers, indicating that urban sources may affect water quality in the catchment area substantially. However, it was observed that pesticide substances remain in the soil over a long time supported by sorption on the soil matrix. Therefore, delayed inputs into surface waters could be suspected. For the implementation of reduction measures, both urban and agricultural sources should be considered. Novel findings of the study: pesticide detections were not consistent with application data from farmers, urban sources contributed substantially to pesticide pollution of surface waters.

Leaching and degradation of 13C2-15N-glyphosate in field lysimeters.

Glyphosate (GLYP), the globally most important herbicide, may have effects in various compartments of the environment such as soil and water. Although laboratory studies showed fast microbial degradation and a low leaching potential, it is often detected in various environmental compartments, but pathways are unknown. Therefore, the objective was to study GLYP leaching and transformations in a lysimeter field experiment over a study period of one hydrological year using non-radioactive 13C2-15N-GLYP labelling and maize cultivation. 15N and 13C were selectively measured using isotopic ratio mass spectrometry (IR-MS) in leachates, soil, and plant material. Additionally, HPLC coupled to tandem mass spectrometry (HPLC-MS/MS) was used for quantitation of GLYP and its main degradation product aminomethylphosphonic acid (AMPA) in different environmental compartments (leachates and soil). Results show low recoveries for GLYP (< 3%) and AMPA (< level of detection) in soil after the study period, whereas recoveries of 15N (11-19%) and 13C (23-54%) were higher. Time independent enrichment of 15N and 13C and the absence of GLYP and AMPA in leachates indicated further degradation. 15N was enriched in all compartments of maize plants (roots, shoots, and cobs). 13C was only enriched in roots. Results confirmed rapid degradation to further degradation products, e.g., 15NH4+, which plausibly was taken up as nutrient by plants. Due to the discrepancy of low GLYP and AMPA concentrations in soil, but higher values for 15N and 13C after the study period, it cannot be excluded that non-extractable residues of GLYP remained and accumulated in soil.

A New Principle for Measuring the Average Relative Humidity in Large Volumes of Non-Homogenous Gas.

Due to the current extent of arid regions, the pressure on available water resources is increasing. A suitable measure for water availability and dynamics in dry soil is the relative humidity of the soil air. Due to the heterogeneity of soil, water inputs, and root water uptake, the humidity of soil air will vary in space. Therefore, area-representative measurement methods are needed to find a representative measure of the soil water status. Existing sensors for the direct determination of relative humidity only represent a single location with a spatial extent of up to several cm. We introduce a new measuring principle that averages over a spatially heterogeneously distributed relative humidity. It is based on the selective diffusion of water vapor pressure through a tubular semipermeable membrane to/from a closed measurement chamber. A measured pressure change is sensitive to the water vapor pressure and enables, without any external calibration, to estimate an average of the relative humidity. The comparison of our first laboratory prototype of the new sensor with calibrated reference sensors for relative humidity in a range of approx. 4 to 100% proves the linearity of the measuring method and its high accuracy. For further optimization improved reference measurement techniques are necessary. A potential application is the improvement of water use efficiency in irrigated agriculture.

Plant available phosphorus in soil as predictor for the leaching potential: Insights from long-term lysimeter studies.

This study aimed to demonstrate the impact of phosphorus (P) mineral fertilization on topsoil P content and P leaching. We evaluated 83 datasets from 25 years from lysimeter experiments involving different cropping systems (winter crop, summer crop and autumn tillage, harvested grass) or unfertilized fallow, four types of soil texture, and three levels of applied mineral P fertilizer. A positive monotonic and significant correlation was indicated between P in the topsoil determined by the double lactate method (P DL) and the yearly flow-weight total (TP) concentrations in leachates with Spearman rank correlations r s (r s > 0.183) and probability (p) < 0.05. The present German recommended rates of P mineral fertilization are proposed insufficient to protect fresh and marine waters from undesired P pollution and eutrophication. A long-term reduction of excess soil P is urgent along with other measures to mitigate high P inputs to surface and ground waters.

Impact of raking and bioturbation-mediated ecological manipulation on sediment-water phosphorus diagenesis: a mesocosm study supported with radioactive signature.

The study examined the impact of raking and fish bioturbation on modulating phosphorus (P) concentrations in the water and sediment under different trophic conditions. An outdoor experiment was set to monitor physicochemical and microbiological parameters of water and sediment influencing P diagenesis. A pilot study with radioactive 32P was also performed under the agency of raking and bacteria (Bacillus sp.). Raking was more effective in release of P under unfertilized conditions by significantly enhancing orthophosphate (35%) and soluble reactive phosphate (31.8%) over respective controls. Bioturbation increased total and available P in sediments significantly as compared to control. The rates of increase were higher in the unfertilized conditions (17.6-28.4% for total P and 12.2 to 23.2% for available P) than the fertilized ones (6.5-12.4% for total P and 9.1 to 15% for available P). The combined effects of raking and bioturbation on orthophosphate and soluble reactive phosphate were also stronger under unfertilized state (54.5 and 81.8%) than fertilized ones (50 and 70%). The tracer signature showed that coupled action of introduced bacteria and repeated raking resulted in 59.2, 23 and 16% higher counts of radioactive P than the treatments receiving raking once, repeated raking and bacteria inoculation, respectively. Raking alone or in sync with bioturbation exerted pronounced impact on P diagenesis through induction of coupled mineralization and nutrient release. It has significant implication for performing regular raking of fish-farm sediments and manipulation of bottom-grazing fish to regulate mineralization of organic matter and release of obnoxious gases from the system. Further, they synergistically can enhance the buffering capacity against organic overload and help to maintain aquatic ecosystem health.

Differences in DOM of rewetted and natural peatlands - Results from high-field FT-ICR-MS and bulk optical parameters.

Peatlands can be a potential source of dissolved organic matter (DOM) in fresh water catchment areas. The quantity and quality of DOM can differ between pristine, degraded and rewetted peatlands. Due to the large scale and continuing losses of peatlands, their conservation and restoration has been increasingly emphasized. Mostly rewetting measures are required to improve the hydrology of damaged peatlands, which is a precondition for the resettlement of peat-forming plant species. Thus, in term of DOM, there is a special need to understand how rewetting measures affect DOM characteristics and concentrations. To estimate the potential leaching of humic substances from rewetted areas two natural sites were compared with four artificially rewetted sites in a peatland area of the Harz Mountains National Park, Germany. This was done with regards to DOM quality by combining the results from Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS, measured at one time in Spring) and excitation-emission-matrix fluorescence spectroscopy (EEMF, measured monthly for the period of one year). The DOM quality was significantly less variable in the pristine peatland soil water compared to the rewetted peatland soil waters, from both a spatial and a seasonal perspective. The soil water from the rewetted peatland sites showed a higher degree of humification compared to pristine peatland. DOC concentration was mostly consistent in the pristine peatland over the year. The rewetted peatlands showed higher DOC levels in Summer months and lower DOC in Winter months compared to the pristine peatland. It can be concluded that the rewetting of peatlands is coupled with high concentrations of DOC in soil water and its quality is highly aromatic (as reflected by the observed values from the humification index) during times with elevated temperature. The results may have a significant input for dynamic catchment area studies with regards to rewetting peatland sites.

Release of nitrous oxide and dinitrogen from a transition bog under drained and rewetted conditions due to denitrification: results from a [15N]nitrate-bromide double-tracer study.

Denitrification is well known being the most important nitrate-consuming process in water-logged peat soils, whereby the intermediate compound nitrous oxide (N(2)O) and the end product dinitrogen (N(2)) are ultimately released. The present study was aimed at evaluating the release of these gases (due to denitrification) from a nutrient-poor transition bog ecosystem under drained and three differently rewetted conditions at the field scale using a (15)N-tracer approach ([(15)N]nitrate application, 30 kg N ha(-1)) and a common closed-chamber technique. The drained site is characterized by a constant water table (WT) of -30 cm (here referred to as D30), while rewetted sites represent a constant WT of -15 cm, a constant WT of 0 cm (i.e. waterlogged), and an initial WT of 0 cm (which decreased slightly during the experiment), respectively, (here referred to as R15, R0, and R0(d), respectively). The highest N(2)O emissions were observed at D30 (291 µg N(2)O-N m(-2) h(-1)) as well as at R0d (665 µg N(2)O-N m(-2) h(-1)). At the rewetted peat sites with a constant WT (i.e. R15 and R0), considerably lower N2O emissions were observed (maximal 37 µg N(2)O-N m(-2) h(-1)). Concerning N(2) only at the initially water-logged peat site R0d considerable release rates (up to 3110 µg N(2)-N m(-2) h(-1)) were observed, while under drained conditions (D30) no N(2) emission and under rewetted conditions with a constant WT (R15 and R0) significantly lower N(2) release rates (maximal 668 µg N(2)-N m(-2) h(-1)) could be detected. In addition, it has been found that natural WT fluctuations at rewetted peat sites, in particular a rapid drop down of the WT, can induce high emission rates for both N(2)O and N(2).

Temporal dynamics of pore water concentrations of Cd, Co, Cu, Ni, and Zn and their controlling factors in a contaminated floodplain soil assessed by undisturbed groundwater lysimeters.

We aimed to assess the dynamics of pore water concentrations of Cd, Co, Cu, Ni, Zn and their controlling factors (EH, pH, DOC, Fe, Mn, and SO4(2-)) in a contaminated floodplain soil under different flood-dry-cycles. Two parallel undisturbed groundwater lysimeters (mean values presented) were used for long term (LT; 94 days) and short term (ST; 21 days) flood-dry-cycles. Reducing conditions under LT lead to low EH and pH, while DOC, Co, Fe, Mn, and Ni increased. Cadmium, Cu, Zn, and SO4(2-) increased under oxidizing conditions during ST. Cobalt and Ni revealed a similar behavior which seem to governed by EH/pH, Mn, Fe, and DOC. Cadmium, Cu, and Zn reveal a similar fate; their dynamics were affected by EH/pH, DOC, and SO4(2-). Our findings suggest that a release of Cd, Cu, Co, Fe, Mn, Ni, and Zn under different flood-dry-cycles can assumed what might create potential environmental risks in using metal-enriched floodplain soils.

Nitrate turnover in a peat soil under drained and rewetted conditions: results from a [(15)N]nitrate-bromide double-tracer study.

Under natural conditions, peatlands are generally nitrate-limited. However, recent concerns about an additional N input into peatlands by atmospheric N deposition have highlighted the risk of an increased denitrification activity and hence the likelihood of a rise of emissions of the greenhouse gas nitrous oxide. Therefore, the aim of the present study was to investigate the turnover of added nitrate in a drained and a rewetted peatland using a [(15)N]nitrate-bromide double-tracer method. The double-tracer method allows a separation between physical effects (dilution, dispersion and dislocation) and microbial and chemical nitrate transformation by comparing with the conservative Br(-) tracer. In the drained peat site, low NO3(-) consumption rates have been observed. In contrast, NO3(-) consumption at the rewetted peat site rises rapidly to about 100% within 4 days after tracer application. Concomitantly, the (15)N abundances of nitrite and ammonium in soil water increased and lead to the conclusion that, besides commonly known NO3(-) reduction to nitrite (i.e. denitrification), a dissimilatory nitrate reduction to ammonium has simultaneously taken place. The present study reveals that increasing NO3(-) inputs into rewetted peatlands via atmospheric deposition results in a rapid NO3(-) consumption, which could lead to an increase in N2O emissions into the atmosphere.

Trace metals accumulation in Bacopa monnieri and their bioaccessibility.

Bacopa monnieri is commonly known as "Brahmi" or "Water hyssop" and is a source of nootropic drugs. Aboveground parts of plant samples collected from peri-urban Indian areas were analysed for total trace metal concentrations. Subsequently, three samples with high concentrations of Cd and Pb were subjected to in vitro gastrointestinal digestion to assess the bioaccessibility of the trace metals in these plants. The total concentrations of trace metals on a dry weight basis were 1.3 to 6.7 mg·kg⁻¹ Cd, 1.5 to 22 mg·kg⁻¹ Pb, 36 to 237 mg·kg⁻¹ Cu, and 78 to 186 mg·kg⁻¹ Zn. The majority of Bacopa monnieri samples exceeded threshold limits of Cd, Pb, Cu, and Zn for use as raw medicinal plant material or direct consumption. Therefore, it is necessary to evaluate Bacopa monnieri collected in nature for their trace metal content prior to human consumption and preparation of herbal formulations.

Analysis of the effect of meteorological factors on dewfall.

To get an insight into when dewfall will occur and how much to expect we carried out extensive calculations with the energy balance equation for a crop surface to 1) identify the meteorological factors which determine dewfall, 2) establish the relationship between dewfall and each of them, and 3) analyse how these relationships are influenced by changes in these factors. The meteorological factors which determine dewfall were found to be air temperature (T(a)), cloud cover (N), wind speed (u), soil heat flux (G), and relative humidity (h(r)). Net radiation is also a relevant factor. We did not consider it explicitly, but indirectly through the effect of temperature on the night-time radiation balance. The temperature of the surface (T(s)) where dew forms on is also important. However, it is not a meteorological factor, but determined by the aforementioned parameters. All other conditions being equal our study revealed that dewfall increases linearly with decreasing N or G, and with increasing h(r). The effect of T(a) and u on dewfall is non-linear: dewfall initially increases with increasing T(a) or u, and then decreases. All five meteorological factors can lead to variations in dewfall between 0 and 25 W m(-2) over the range of their values we studied. The magnitude of the variation due to one factor depends on the value of the others. Dewfall is highest at N=0, G=0, and h(r)=1. Ta at which dewfall is highest depends on u and vice versa. The change in dewfall for a unit change in N, G or h(r) is not affected by the value of N, G or h(r), but increases as T(a) or u increase. The change in dewfall for a unit change in Ta or u depends on the value of the other four meteorological factors.

Spatial distribution of arsenic and heavy metals in willow roots from a contaminated floodplain soil measured by X-ray fluorescence spectroscopy.

Under changing redox conditions some plants create plaques at their root surface, which may affect the mobility and uptake of As and heavy metals but it is unknown to what extent this also holds true for willows in contaminated floodplain soils. Therefore, willow roots were sampled from a phytoremediation trial in the contaminated floodplain of the river Elbe (Germany), cryofixed, freeze-dried, and cross sections were mapped for the distribution of As, Ca, Cu, Fe, K, Mn, Ni, S and Zn by synchrotron based X-ray fluorescence spectroscopy. The elements Ca, Cu, Ni, S and Zn were concentrated in the aerenchymatic tissue, and not associated with Fe and Mn. Mixed Fe-Mn plaques covered the surface of the willow roots and As was accumulated in these plaques. The observed association pattern between As and Fe was explained by the different sorption/desorption properties of As(III) and As(V). The Cu and Zn intensities were not associated with the intensity of Fe in the plaque, which seems to be a willow-specific difference compared to other wetland plants. These results suggested that willows are especially suited to stabilize low-phytoextractable elements like Cu and As in their roots and rhizosphere. Thus, short rotation coppicing of willows may be a practical approach to mitigate the adverse effects of floodplain soil contamination.

Small scale variability of chlorinated POPs in the river Elbe floodplain soils (Germany).

The long-time use of persistent organic pollutants (POPs) led to a world-wide contamination of environmental compartments. Although, bans of numerous POPs reduced the POP input to rivers. Floodplain soils are still highly contaminated, because they are sinks for these compounds, which restrict their agricultural use. Hence, the intention of this study was the determination of 29 relevant POPs in two soil depths (0-10 cm and 10-20 cm) of a field experiment to get a survey on the small-scale spatial variability of the experimental site and to establish a baseline for phytoremediation experiments. The POP concentrations ranged from 0.1 microg kg(-1) to 160 microg kg(-1) and showed an increase of dieldrin, endrin, endosulfan I, endosulfan II, heptachlor, p,p'-DDE, o,p'-DDE and methoxychlor concentrations on average in the river Elbe floodplains between the years 1998 and 2007. However, there was a pronounced small-scale spatial variability of POP concentrations in vertical and horizontal direction. The latter was estimated by comparing the relative standard deviations (RSDs) of the POP concentrations in sample sets located at sites of increasing distance from <1m to >10000 m.

ASSOCIATED BACTERIA INCREASE THE PHYTOEXTRACTION OF CADMIUM AND ZINC FROM A METAL-CONTAMINATED SOIL BY MYCORRHIZAL WILLOWS.

In order to enhance phytoremediation efficiency, we investigated the effects of dual inoculation with ectomycorrhizal fungi and the ectomycorrhiza associated bacteria Micrococcus luteus and Sphingomonas sp. on the growth and metal accumulation of willows (Salix viminalis x caprea) on contaminated soil. The bacterial strains were previously collected from sporocarps of ectomycorrhizal fungi. The bacteria increased plant growth and the mycorrhizal dependency of willows colonized with the ectomycorrhizal fungus Hebeloma crustuliniforme. The total cadmium (Cd) and zinc (Zn) accumulation in the shoot biomass was increased after inoculation with the fungal strain Hebeloma crustuliniforme in combination with Micrococcus luteus up to 53% and in combination with Sphingomonas sp. up to 62%, respectively. The dual inoculation in combination with Laccaria laccata did not increase the accumulation of Cd and Zn in the willows. We conclude that associated bacteria can enhance the ectomyorrhiza formation and growth of willows and, thereby, the Cd and Zn accumulation in the plant biomass. The results suggest that bacterial support of root growth promoting ectomycorrhizal fungi may be a promising approach to improve the remediation of metal-contaminated soils by using willows.