On-Site Sensor Calibration Procedure for Quality Assurance of Barometric Process Separation (BaPS) Measurements.

Barometric process separation (BaPS) is an automated laboratory system for the simultaneous measurement of microbial respiration and gross nitrification rates in soil samples. To ensure optimal functioning, the sensor system, consisting of a pressure sensor, an O2 sensor, a CO2 concentration sensor, and two temperature probes, must be accurately calibrated. For the regular on-site quality control of the sensors, we developed easy, inexpensive, and flexible calibration procedures. The pressure sensor was calibrated by means of a differential manometer. The O2 and CO2 sensors were simultaneously calibrated through their exposure to a sequence of O2 and CO2 concentrations obtained by sequentially exchanging O2/N2 and CO2/N2 calibration gases. Linear regression models were best suited for describing the recorded calibration data. The accuracy of O2 and CO2 calibration was mainly affected by the accuracy of the utilized gas mixtures. Because the applied measuring method is based on the O2 conductivity of ZrO2, the O2 sensor is particularly susceptible to aging and to consequent signal shifts. Sensor signals were characterized by high temporal stability over the years. Deviations in the calibration parameters affected the measured gross nitrification rate by up to 12.5% and affected the respiration rate by up to 5%. Overall, the proposed calibration procedures are valuable tools for ensuring the quality of BaPS measurements and for promptly identifying sensor malfunctions.

Does silica addition affect translocation and leaching of cadmium and copper in soil?

Soil and groundwater contamination with potentially toxic elements (PTEs) including cadmium (Cd) and copper (Cu) has become a serious problem for ecosystem functioning. Silicon (Si) may precipitate these metals as silicates, and may also form, at undersaturation of silicates, 'Si-contaminant compounds', i.e. particles of polymerized silica with PTEs incorporated or adsorbed by inner-sphere complexes. While the formation of these compounds in aqueous solution has been proven, their formation in soil remains unclear yet. Therefore, we conducted column experiments with a topsoil horizon artificially contaminated with Cd or Cu solutions (10 mM) in the presence (10 mM) and absence of monomeric Si, and monitored the elemental composition of the eluates during 12 irrigation steps with artificial rainwater by microwave-plasma atomic emission spectrometry, the size and charge of the particles eluted by dynamic light scattering and phase analysis light scattering, and determined the spatial distribution of total and exchangeable Cd and Cu in soil after the experiments. When Si was previously applied to soil, significantly larger particles (up to > 200 nm) in the eluates indicated Si polymerization and formation of Si-contaminant compounds. However, Cd and Cu concentrations were very low (<0.4 µM), pointing to efficient retardation in soil. In any variant, the particles formed were slightly negatively charged (-11 mV). The molar metal:Si ratios in the eluates and significant correlations between the amounts of Si and metals in soil extracted by NH4NO3 pointed to the formation of Si-contaminant compounds, too. More Cu than Cd was retained in soil, and significantly more in the presence of Si, but less Cu than Cd was in exchangeable form. While particularly Cu formed Si-contaminant compounds, which reduced the concentration of Cu ions, the Si-contaminant-compound particles in the eluates remained very small, thus potentially susceptible to particulate export from soil into the groundwater.

Altered energy partitioning across terrestrial ecosystems in the European drought year 2018.

Drought and heat events, such as the 2018 European drought, interact with the exchange of energy between the land surface and the atmosphere, potentially affecting albedo, sensible and latent heat fluxes, as well as CO2 exchange. Each of these quantities may aggravate or mitigate the drought, heat, their side effects on productivity, water scarcity and global warming. We used measurements of 56 eddy covariance sites across Europe to examine the response of fluxes to extreme drought prevailing most of the year 2018 and how the response differed across various ecosystem types (forests, grasslands, croplands and peatlands). Each component of the surface radiation and energy balance observed in 2018 was compared to available data per site during a reference period 2004-2017. Based on anomalies in precipitation and reference evapotranspiration, we classified 46 sites as drought affected. These received on average 9% more solar radiation and released 32% more sensible heat to the atmosphere compared to the mean of the reference period. In general, drought decreased net CO2 uptake by 17.8%, but did not significantly change net evapotranspiration. The response of these fluxes differed characteristically between ecosystems; in particular, the general increase in the evaporative index was strongest in peatlands and weakest in croplands. This article is part of the theme issue 'Impacts of the 2018 severe drought and heatwave in Europe: from site to continental scale'.

Contribution of plant-induced pressurized flow to CH4 emission from a Phragmites fen.

The widespread wetland species Phragmites australis (Cav.) Trin. ex Steud. has the ability to transport gases through its stems via a pressurized flow. This results in a high oxygen (O2) transport to the rhizosphere, suppressing methane (CH4) production and stimulating CH4 oxidation. Simultaneously CH4 is transported in the opposite direction to the atmosphere, bypassing the oxic surface layer. This raises the question how this plant-mediated gas transport in Phragmites affects the net CH4 emission. A field experiment was set-up in a Phragmites-dominated fen in Germany, to determine the contribution of all three gas transport pathways (plant-mediated, diffusive and ebullition) during the growth stage of Phragmites from intact vegetation (control), from clipped stems (CR) to exclude the pressurized flow, and from clipped and sealed stems (CSR) to exclude any plant-transport. Clipping resulted in a 60% reduced diffusive + plant-mediated flux (control: 517, CR: 217, CSR: 279 mg CH4 m-2 day-1). Simultaneously, ebullition strongly increased by a factor of 7-13 (control: 10, CR: 71, CSR: 126 mg CH4 m-2 day-1). This increase of ebullition did, however, not compensate for the exclusion of pressurized flow. Total CH4 emission from the control was 2.3 and 1.3 times higher than from CR and CSR respectively, demonstrating the significant role of pressurized gas transport in Phragmites-stands.

Multimodel ensembles of wheat growth: many models are better than one.

Crop models of crop growth are increasingly used to quantify the impact of global changes due to climate or crop management. Therefore, accuracy of simulation results is a major concern. Studies with ensembles of crop models can give valuable information about model accuracy and uncertainty, but such studies are difficult to organize and have only recently begun. We report on the largest ensemble study to date, of 27 wheat models tested in four contrasting locations for their accuracy in simulating multiple crop growth and yield variables. The relative error averaged over models was 24-38% for the different end-of-season variables including grain yield (GY) and grain protein concentration (GPC). There was little relation between error of a model for GY or GPC and error for in-season variables. Thus, most models did not arrive at accurate simulations of GY and GPC by accurately simulating preceding growth dynamics. Ensemble simulations, taking either the mean (e-mean) or median (e-median) of simulated values, gave better estimates than any individual model when all variables were considered. Compared to individual models, e-median ranked first in simulating measured GY and third in GPC. The error of e-mean and e-median declined with an increasing number of ensemble members, with little decrease beyond 10 models. We conclude that multimodel ensembles can be used to create new estimators with improved accuracy and consistency in simulating growth dynamics. We argue that these results are applicable to other crop species, and hypothesize that they apply more generally to ecological system models.

Pesticide transport pathways from a sloped Litchi orchard to an adjacent tropical stream as identified by hydrograph separation.

This study was performed to identify the transport pathways of pesticides from a sloped litchi ( Sonn.) orchard to a nearby stream based on a three-component hydrograph separation (baseflow, interflow, surface runoff). Dissolved silica and electrical conductivity were chosen as representative tracers. During the study period (30 d), 0.4 and 0.01% of the applied mass of atrazine and chlorpyrifos, respectively, were detected in the stream after 151 mm of rainfall. Baseflow (80-96%) was the dominant hydrological flow component, followed by interflow (3-18%) and surface runoff (1-7%). Despite its small contribution to total discharge, surface runoff was the dominant atrazine transport pathway during the first days after application because pesticide concentrations in the surface runoff flow component declined quickly within several days. Preferential transport with interflow became the dominant pathway of atrazine. Because chlorpyrifos was detected in the stream water only twice, it was not included in the hydrograph separation. A feature of the surface runoff pathway was the coincidence of pesticide and discharge peaks. In contrast, peak concentrations of pesticides transported by interflow occurred during the hydrograph recession phases. Stormflow generation and pesticide transport depended on antecedent rainfall. The combination of high-resolution pesticide concentration measurements with a three-component hydrograph separation has been shown to be a suitable method to identify pesticide transport pathways under tropical conditions.

Modeling concentration-dependent sorption-desorption hysteresis of atrazine in a loam soil.

Nonequilibrium sorption plays an active role in the transport of organic contaminants in soil. We applied a two-stage, one-rate model (2S1R) and a new, nonlinear variant (2S1RN) of this model to examine the effects of wastewater irrigation on the sorption kinetics of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) in soil. The models were applied to previously published sorption-desorption data sets, which showed pronounced deviations between sorption curves and desorption curves (sorption-desorption hysteresis). Moreover, the slopes of the desorption curves decreased with decreasing concentration. Different treatments had been used, and two experimental time steps (2 and 14 d) were used. Treatments considered were lipid removal, fulvic and humic acid removal, and untreated soil. The 2S1R model was unable to reproduce the observed type of hysteresis, but the 2S1RN model, which assumes that the sorption-desorption process follows a power function relationship, was able to reproduce the observed type of hysteresis. Visually, applying the new model improved the model fits in all test cases. Statistically, as tested by an extra sum of squares analysis, the new model performed significantly better in 50% of all test cases. According to an example simulation, the choice of the sorption model has a considerable impact on the prediction of atrazine transport in soil.

Cadmium leaching from micro-lysimeters planted with the hyperaccumulator Thlaspi caerulescens: experimental findings and modeling.

The use of heavy metal hyperaccumulating plants has the potential to become a promising new technique to remediate contaminated sites. We investigated the role of metal mobilization in the Cd hyperaccumulation of Thlaspi caerulescens (J. & C. Presl, 'Ganges'). In a micro-lysimeter experiment we investigated the dynamics of Cd concentration of leachate as well as Cd removal by plant uptake in four treatments: (i) Control (bare soil), (ii) T. caerulescens, (iii) nonhyperaccumulator Brassica juncea (L.) Czern. ('PI 426308'), and (iv) co-cropping of the hyperaccumulator and nonhyperaccumulator. The experimental findings were analyzed using one- and two-site rate-limited desorption models. Co-cropping of T. caerulescens and B. juncea did not enhance metal uptake by B. juncea. Although Cd uptake of T. caerulescens was 10 times higher than that of B. juncea, the Cd concentration of leachate of the T. caerulescens treatment did not decrease below that of the B. juncea treatment. The Cd depletion in leachate was well reproduced by the two-site rate-limited desorption model. The optimized desorption coefficient was three orders of magnitude higher in the rhizosphere than in the bulk soil. Our results indicate that T. caerulescens accelerates the resupply of Cd from soil pointing to an important role of kinetic desorption in the hyperaccumulation by T. caerulescens.

Modeling the environmental fate of cadmium in a large wastewater irrigation area.

The fate of cadmium in soils is governed by spatially heterogeneous processes that proceed from decades to centuries. This study aimed at modeling the fate of Cd within the wastewater irrigation area (WIA) of Braunschweig (Germany). The sandy soils (mainly Dystric Cambisol or Typic Haplumbrept) at this site (28 km2) have received considerable loads of heavy metals by irrigation of municipal wastewater for up to 40 yr. The soils of the WIA are in agricultural use. The main crops are sugar beet (Beta vulgaris L.), potato (Solanum tuberosum L.), and wheat (Triticum aestivum L.). As a result of asparagus (Asparagus officinalis L.) cropping, about 15% of the soils have been converted to Rigosols. In 1996, we measured the vertical distribution (0 to 1.2 m) of soil pH, organic carbon content, and the EDTA-extractable content and the solution phase concentration of Cd at 153 sites. At sites not used for asparagus cultivation, Cd has migrated on average to a depth of about 0.5 m. Due to deep plowing, which accelerates migration, Cd has been displaced on average to about 0.7 m at the Rigosol sites. To model the fate of Cd at the scale of the WIA, we used different parallel soil column approaches. In each column the local model SEFAH was used to simulate both displacement and plant uptake of Cd. The model was fed with measured or randomly generated soil data. The results of retrospective simulations from 1957 to 1996 agreed well with observed Cd profiles. The better the spatial variability of sorption was described, the better the performance. Our simulation results show that Cd pollution of soil at first affects the soil-plant pathway. The breakthrough of Cd to the groundwater is dampened and is delayed for many decades.

A regional-scale study on the crop uptake of cadmium from sandy soils: measurement and modeling.

Plant uptake is one of the major pathways by which cadmium (Cd) in soils enters the human food chain. This study was conducted to investigate the uptake of Cd by crops from soils within the wastewater irrigation area (WIA) of Braunschweig (Germany) and to develop a simple process-oriented model that is suited to predict Cd uptake at the regional scale. The sandy soils within the WIA (4300 ha) have received considerable loads of heavy metals by irrigation using municipal wastewater for up to 40 years. In 1998 and 1999, we sampled soil and plant material at 40 potato (Solanum tuberosum L.), 40 sugar beet (Beta vulgaris L.), and 32 winter wheat (Triticum aestivum L.) fields. In both years and for all three crops, we found close linear relationships between the Cd content of plant material and the Cd concentration in soil solution. For all three crops, we observed a trend of relatively increased Cd uptake in the year with the higher saturation deficit of the atmosphere. We interpret this to indicate that transpiration plays an important role in the Cd uptake of crops under the conditions of the WIA. In modeling the uptake of Cd by crops, we assume that uptake is proportional to mass flow, that is, the product of water transpired, Cd concentration in soil solution, and a plant-specific empirical parameter. The simulations agreed well with the observed Cd contents in crops. Our model explained between 66 and 87% of the observed variance.