Comparison of methods for measuring heavy metals and total phosphorus in soils contaminated by different sources

The relationships between the concentrations of zinc (Zn), lead (Pb), copper (Cu), nickel (Ni) and chromium (Cr) as measured by X-ray fluorescence analysis (XRF), aqua regia, and HNO₃ pressure digestion were studied in soil samples covering a wide range of heavy metal concentrations. The soils were contaminated by sewage sludge, exhaust depositions, river sediments of mining residues, and dump material. The question was addressed whether the source of heavy metals or other soil properties affect the relationship between these three methods. The aqua regia-digestible fraction of the five heavy metals reached on average 64% of the XRF-detectable content. The pressure accelerated HNO₃-digestible fraction of the five heavy metals was on average 71% of the XRF-detectable content; the respective phosphorus (P) fraction reached a median of 75%. This suggests that HNO₃ pressure digestion can also be used for characterizing the total P content of soils. Aqua regia extraction and HNO₃ pressure digestion gave similar values for Zn, Pb, and Cu, which dominate the heavy metal load of most contamination sources. Significantly higher Cr values were obtained by HNO₃ pressure digestion than by aqua regia extraction. Additionally, the Cr contents were affected by the source, e.g. sewage sludge had relatively high contents of aqua regia and HNO₃ pressure extractable contents in comparison to the XRF values. The element-specific relationships between the three methods were all highly significant. However, the respective multiple linear regression models were in most cases affected by soil organic carbon (C), in some cases by clay or soil pH.     

Microbial C,N, and P relationships in moisture‐stressed soils of Potohar,Pakistan

In 11 rain‐fed arable soils of the Potohar plateau, Pakistan, the amounts of microbial‐biomass C (C_mic), biomass N (N_mic), and biomass P (P_mic) were analyzed in relation to the element‐specific total storage compartment, i.e., soil C_org, N_t, and P_t. The effects of climatic conditions and soil physico‐chemical properties on these relationships were highlighted with special respect to crop yield levels. Average contents of soil C_org, N_t, and P_t were 3.9, 0.32, and 0.61 mg (g soil)^–1, respectively. Less than 1% of P_t was extractable with 0.5 M NaHCO₃. Mean contents of C_mic, N_mic, and P_mic were 118.4, 12.0, and 3.9 µg (g soil)^–1. Values of C_mic, N_mic, P_mic, soil C_org, and N_t were all highly significantly interrelated. The mean crop yield level was closely connected with all soil organic matter– and microbial biomass–related properties, but showed also some influence by the amount of precipitation from September to June. Also the fraction of NaHCO₃‐extractable P was closely related to soil organic matter, soil microbial biomass, and crop yield level. This reveals the overwhelming importance of biological processes for P turnover in alkaline soils.     

A Laboratory Study on Revegetation and Metal Uptake in Native Plant Species from Neutral Mine Tailings

Lygeum spartum, Zygophyllum fabago and Piptatherum miliaceum are typical plant species that grow in mine tailings in semiarid Mediterranean areas. The aim of this work was to investigate metal uptake of these species growing on neutral mine tailings under controlled conditions and their response to fertilizer additions. A neutral mine tailing (pH of soil solution of 7.1–7.2) with high total metal concentrations (9,100 and 5,200 mg kg^?1 Zn and Pb, respectively) from Southern Spain was used. Soluble Zn and Pb were low (0.5 and <0.1 mg l^?1, respectively) but the major cations and anions reached relatively high levels (e.g. 2,600 and 1,400 mg l^?1 Cl and Na). Fertilization caused a significant increase of the plant weight for the three species and decreased metal accumulation with the exception of Cd. Roots accumulated much higher metal concentrations for the three plants than shoots, except Cd in L. spartum. Shoot concentrations for the three plants were 3–14 mg kg^?1 Cd, 150–300 mg kg^?1 Zn, 4–11 mg kg^?1 Cu, and 1–10 mg kg^?1 As, and 6–110 mg kg^?1 Pb. The results indicate that neutral pH mine tailings present a suitable substrate for establishment of these native plants species and fertilizer favors this establishment. Metal accumulation in plants is relatively low despite high total soil concentrations.     

Rate of soil‐aggregate formation under different organic matter amendments—a short‐term incubation experiment

To improve soil structure and take advantage of several accompanying ecological benefits, it is necessary to understand the underlying processes of aggregate dynamics in soils. Our objective was to quantify macroaggregate (> 250 μm) rebuilding in soils from loess (Haplic Luvisol) with different initial soil organic C (SOC) contents and different amendments of organic matter (OM) in a short term incubation experiment. Two soils differing in C content and sampled at 0–5 and 5–25 cm soil depths were incubated after macroaggregate destruction. The following treatments were applied: (1) control (without any addition), (2) OM₁ (addition of OM: preincubated wheat straw [< 10 mm, C : N 40.6] at a rate of 4.1 g C [kg soil]^–1), and (3) OM₂ (same as (2) at a rate of 8.2 g C [kg soil]^–1). Evolution of CO₂ released from the treatments was measured continuously, and contents of different water‐stable aggregate‐size classes (> 250 μm, 250–53 μm, < 53 μm), microbial biomass, and ergosterol were determined after 7 and 28 d of incubation. Highest microbial activity was observed in the first 3 d after the OM application. With one exception, > 50% of the rebuilt macroaggregates were formed within the first 7 d after rewetting and addition of OM. However, the amount of organic C within the new macroaggregates was ≈ 2‐ to 3‐fold higher than in the original soil. The process of aggregate formation was still proceeding after 7 d of incubation, however at a lower rate. Contents of organic C within macroaggregates were decreased markedly after 28 d of incubation in the OM₁ and OM₂ treatments, suggesting that the microbial biomass (bacteria and fungi) used organic C within the newly built macroaggregates. Overall, the results confirmed for all treatments that macroaggregate formation is a rapid process and highly connected with the amount of OM added and microbial activity. However, the time of maximum aggregation after C addition depends on the soil and substrate investigated. Moreover, the results suggest that the primary macroaggregates, formed within the first 7 d, are still unstable and oversaturated with OM and therefore act as C source for microbial decomposition processes.     

Usefulness of near-infrared spectroscopy to determine biological and chemical soil properties: Importance of sample pre-treatment

Near-infrared reflectance spectroscopy (NIRS) is known for its inexpensiveness, rapidity and accuracy and may become a useful tool for the assessment of soil quality. Objectives were (i) to evaluate the ability of NIRS to predict several chemical and biological properties of organically managed arable soils as well as the properties of grain yield from winter cereals for a closed population and (ii) to test whether the use of field-moist and pre-treated (quick-freezing followed by freeze-drying and grinding) samples will generate similar results. One hundred and sixteen soil samples from nine organically managed farms from Germany sampled in 2005 and 2006 were used for this investigation. Spectra of the near-infrared region (including the visible range, 400–2500 nm) from field-moist (<2 mm) or pre-treated soil samples were recorded. A modified partial least-square regression method and cross-validation were used to develop an equation over the whole spectrum (first–third derivation). For the pre-treated soils, good predictions were obtained for pH, contents of organic C, total N, plant-available P (Olsen) and exchangeable K (calcium-acetate-lactate (CAL)), contents of microbial biomass C and N (C_mic and N_mic) and ergosterol, basal respiration, metabolic quotient, the ratio of organic C/total N, the grain yield of winter cereals and grain nitrogen uptake. The RSC (the ratio of standard deviation of laboratory results to standard error of cross-validation) was greater than 2.0, the correlation coefficients (r) of a linear regression (measured against predicted values) were greater than or equal to 0.9 and the regression coefficients (a) ranged from 0.9 to 1.1. Similar good predictions were obtained if field-moist samples were used, with the exception of P (Olsen), K (CAL), metabolic quotient, grain yield of winter cereals and grain nitrogen uptake (satisfactory predictions) and ergosterol content (unsatisfactory prediction). Good predictions of the contents of Mg (CaCl₂) and microbial biomass P (P_mic) were achieved for field-moist but not for pre-treated samples. Despite sample preparation, only satisfactory predictions were obtained for the ratios of C_mic/N_mic and ergosterol/C_mic and grain nitrogen content (1.4RSC2.0, r0.8 and 0.8a1.2). However, unsatisfactory predictions for field-moist and pre-treated samples were achieved for the content of P (CAL), the nitrogen mineralisation rate and the ratios of C_mic/P_mic and basal respiration/nitrogen mineralisation rate. Our results demonstrate that biological soil properties can be predicted with NIRS for closed populations in both sample states. The pre-treatment should be used if samples have to be stored prior to infrared measurements for periods longer than a month.     

Indicators for assessing anthropogenic impact on urban surface and groundwater

Background, Aim and Scope  Our study focuses on the indication of anthropogenic impacts on the urban surface and groundwater in large cities, demonstrated for the cities of Halle/Saale and Leipzig (Germany). For the study we selected indicator substances such as xenobiotics, trace elements, and stable isotopes which are connected to human activities in urban areas. The xenobiotics reported here are the pharmaceutical carbamacepine, the polycylic musk compounds galaxolide and tonalide, the life style product caffeine, and industrial chemicals such as bisphenol A and t-nonylphenol. The investigated xenobiotics pose largely unknown risks to human health and the aquatic ecosystem. Trace elements are represented by the rare earth element gadolinium (Gd), used as magnetic resonance imaging contrast substance. Nitrogen isotopes in dissolved nitrate characterize the origin of nitrogen compounds, mixing and reaction processes. Methodology  River water was sampled along the flow path of the rivers Saale and Weisse Elster through the city of Halle/Saale, the rivers Luppe and Weisse Elster through the city of Leipzig. Separate samples were collected from the effluent of the local waste water treatment plants. Groundwater from Quaternary plain aquifers along the rivers and from different urban locations was collected at the same time. The indicators were analysed and assessed according to their sources, concentration and distribution patterns. Results and Discussion  Based on the nitrogen isotopic signature, dissolved nitrate in river water of the Saale was referred mainly to two sources: the effluent of the water treatment plant and a mixture of diffusive inputs from rain water channels, sewage leakages and agriculture activities along the rivers. The Gd anomaly was recognized in surface water of both cities, particularly in the effluent of the water treatment plants, but clearly attenuated in groundwater. We measured concentrations of xenobiotics in river and sewer water between 10 and 60,000 ng L⁻¹, and, in groundwater, one order of magnitude lower. Distinctions of xenobiotic patterns were found in river water before and after the effluent of treated waste water into the rivers. Degradation of endocrine disrupters and fragrances, but also persistence of carbamacepine were recognized as essential processes during waste water treatment. At the study site Halle/Saale, mass balances were set up for xenobiotics and water fluxes. Conclusions  At both sites, we demonstrated that indicators such as xenobiotics, gadolinium, and nitrogen isotopes are suitable for assessing anthropogenic impacts on urban water. However, the behaviour of these indicators in surface and groundwater has to be considered according to the different geochemical environments.     

Zur Bedeutung des Aggregierungsgrades für die Spannungsverteilung in strukturierten Böden

The effect of soil aggregation on stress distribution in structured soils The mechanical compressibility of arable soils can be described by preconsolidation load value and by the shear resistance parameters of the bulk soil and single aggregates. In order to quantify the effective stress equation must be also known the hydraulic properties of the soil in dependence of the intensity, kind, and number of loading events. The soil reacts as a rigid body at very fast wheeling speed inclusive a very pronounced stress attenuation in the top soil while stresses will be distributed in the soil threedimensionally to deeper depths at slower speed. These variations can be explained by the mechanical as well as by the hydraulic parameters of the bulk soil and single aggregates. Thus, the pore water pressure value of the bulk soil as a parameter of the effective stress equation further depends on the hydraulic properties of the inter- and intraaggregate pore system and continuity. As can be derived from the results the pore water pressure values are identical irrespective of the predessication for clayey polyhedres at high load while in coarse textured prisms the pore water pressure value depends on load and predryness. The consequences for soil strength under dynamic loading are shortly discussed.     

Masked mycotoxins: determination of a deoxynivalenol glucoside in artificially and naturally contaminated wheat by liquid chromatography-tandem mass spectrometry

Conjugated mycotoxins, in which the toxin is usually bound to a more polar substance like glucose, are referred to as masked mycotoxins, as these substances escape routine detection methods but can release their toxic precursors after hydrolysis. This is the first report on the natural occurrence of a glucoside of deoxynivalenol (DON) in Fusarium-infected wheat and maize. To obtain appropriate standards, we chemically synthesized deoxynivalenol-3-beta-D-glucopyranoside (DON-3-glucoside) and deoxynivalenol-15-beta-D-glucopyranoside (DON-15-glucoside). The synthesis products were characterized by liquid chromatography-tandem mass spectrometry. The DON-glucosides showed different collision-induced dissociation (CID) fragmentation behaviors and could therefore be distinguished. Wheat plants were either treated with DON (n = 52) or with Fusarium spp. (n = 4) at anthesis, and after harvest, wheat ears were analyzed for DON and DON-glucosides. All 56 treated wheat samples contained DON and a DON-glucoside with the same retention time, molecular mass, and CID fragmentation behavior as the synthetic DON-3-glucoside. Moreover, the DON-glucoside was also found in two out of three analyzed naturally DON-contaminated maize and in five out of five naturally contaminated wheat samples, in a range from 4 to 12% of the DON concentration. To further confirm the identity of the DON-glucoside, the compound was isolated from wheat extracts and characterized as DON-3-glucoside with NMR. The results of this study indicate the importance to consider both DON and DON-3-glucoside with regard to food and feed safety.