Characterizing pesticide sorption and degradation in microscale biopurification systems using column displacement experiments

Biopurification systems treating pesticide contaminated water are very efficient, however they operate as a black box. Processes inside the system are not yet characterized. To optimize the performance, knowledge of degradation and retention processes needs to be generated. Therefore, displacement experiments were carried out for four pesticides (isoproturon, bentazone, metalaxyl, linuron) in columns containing different organic mixtures. Bromide, isoproturon and bentazone breakthrough curves (BTCs) were well described using the convection-dispersion equation (CDE) and a first-order degradation kinetic approach. Metalaxyl and linuron BTCs were well described using the CDE model expanded with Monod-type kinetics. Freundlich sorption, first-order degradation and Monod kinetics coefficients were fitted to the BTCs. Fitted values of the distribution coefficient K_f,column were much lower than those determined from batch experiments. Based on mobility, pesticides were ranked as: bentazone > metalaxyl - isoproturon > linuron. Based on degradability, pesticides were ranked as: linuron > metalaxyl - isoproturon > bentazone.     

Assessing Landscape Functions with Broad-Scale Environmental Data: Insights Gained from a Prototype Development for Europe

We examine the advantages and disadvantages of a methodological framework designed to analyze the poorly understood relationships between the ecosystem properties of large portions of land, and their capacities (stocks) to provide goods and services (flows). These capacities (stocks) are referred to as landscape functions. The core of our assessment is a set of expert- and literature-driven binary links, expressing whether specific land uses or other environmental properties have a supportive or neutral role for given landscape functions. The binary links were applied to the environmental properties of 581 administrative units of Europe with widely differing environmental conditions and this resulted in a spatially explicit landscape function assessment. To check under what circumstances the binary links are able to replace complex interrelations, we compared the landscape function maps with independently generated continent-wide assessments (maps of ecosystem services or environmental parameters/indicators). This rigorous testing revealed that for 9 out of 15 functions the straightforward binary links work satisfactorily and generate plausible geographical patterns. This conclusion holds primarily for production functions. The sensitivity of the nine landscape functions to changes in land use was assessed with four land use scenarios (IPCC SRES). It was found that most European regions maintain their capacity to provide the selected services under any of the four scenarios, although in some cases at other locations within the region. At the proposed continental scale, the selected input parameters are thus valid proxies which can be used to assess the mid-term potential of landscapes to provide goods and services.     

Objectives of public economic policy and the adaptation to climate change

Much can be learned about adaptation by applying structures and methodologies already used in other research fields. This study employs a public economic policy approach to investigate how – or if at all – adaptation should be supported by the public sector. Three different fields of adaptation activity are identified which are especially relevant for government intervention and the study proposes ways in which government intervention could be conducted. The analysis takes into account that developing regions are particularly vulnerable and they have insufficient funds to adequately adapt to climate change.     

Requisite Simplicities to Help Negotiate Complex Problems

Decision makers responsible for natural resource management often complain that science delivers fragmented information that is not useful at the scale of implementation. We offer a way of negotiating complex problems by putting forward a requisite simplicity. A requisite simplicity attempts to discard some detail, while retaining conceptual clarity and scientific rigor, and helps us move to a new position where we can benefit from new knowledge. We illustrate the above using three case studies: elephant densities and vegetation change in a national park, the use of rules of thumb to support decision making in agriculture, and the management of salt in irrigation. We identify potential requisite simplicities that can allow us to generate new understanding, lead to action and provide opportunities for structured learning.     

Transport and degradation of pesticides in a biopurification system under variable flux, part I: A microcosm study

The efficiency of a biopurification system, developed to treat pesticide contaminated water, is to a large extent determined by the chemical and hydraulic load. Insight into the behaviour of pesticides under different fluxes is necessary. The behaviour of metalaxyl, bentazone, linuron, isoproturon and metamitron was studied under three different fluxes with or without the presence of pesticide-primed soil in column experiments. Due to the time-dependent sorption process, retention of the pesticides with intermediate mobility was significantly influenced by the flux. The higher the flux, the slower pesticides will be sorbed, which resulted in a lower retention. Degradation of the intermediate mobile pesticides was also submissive to variations in flux. An increase in flux, led to a decrease in retention, which in turn decreased the opportunity time for biodegradation. Finally, the presence of pesticide-primed soil was only beneficial for the degradation of metalaxyl.     

Flood pulse alterations and productivity of the Tonle Sap ecosystem: a model for impact assessment

Tonle Sap Lake is a large and complex data-deficient ecosystem in the Mekong River Basin. Highly valuable in biodiversity and natural livelihoods capital, it is susceptible to degradation when the flood pulse that drives its productivity is altered as a result of hydropower and irrigation development on the Mekong River. To date, there are no tools to assess the consequences of such flood pulse alterations, leaving the Tonle Sap underrated in water-resources use and planning. A combined ecological-hydrodynamic model is presented for the production potential of the Tonle Sap ecosystem and its likely response to hydrological changes.     

Re-evaluation of the conformational structure of sulfadiazine species using NMR and ab initio DFT studies and its implication on sorption and degradation

In the environment, the sorption and the degradation of organic pollutants are of increasing interest. The investigation of the chemical structures provides a basis for the development of a suitable binding model approach and for the mechanistic understanding of the chemical fate processes. The aim of this study was the identification of different species of the antibiotic compound sulfadiazine (SDZ) using (1)H and (13)C NMR experiments and ab initio density functional theory (DFT) calculations. In the neutral, aprotic solvent dimethylsulfoxide-d(6) (DMSO-d(6)), a new sulfadiazine structure containing an O-H-N hydrogen bond was identified. In the protic solvent water-d(2) and in dependence on pH and the position of the amidogen hydrogen atom nine possible SDZ conformations were analyzed and five structures were identified. Good conformity between theory and calculation of (1)H NMR was observed. Unfortunately, (13)C NMR is not sensitive enough for comparison and differentiation. In order to verify the identified structures, additional NBO/NLMO (natural localized molecular orbital) analyses were conducted (calculation of net atomic charges, bond polarity, atomic valence, and electron delocalization). Finally, conformation optimizations were performed in order to investigate the stability of the SDZ species. We showed that SDZ contains no S=O double bond, but that it has two S-O single bonds. Surprisingly, negative charges were observed at the pyrimidine nitrogen atom. With these results, the known structure of SDZ was revised. Studies of the geometrical structure and the torsion angles showed that SDZ is very flexible and can be easily fitted to the sorbent. These observations would explain the strong sorbance and hence the rapid formation of non-extractable residues in the environment because SDZ acts as a strong ligand. These results show that that the sulfonamide hydrogen is important for the biological activity but the pyrimidine nitrogen and the sulfonamide oxygen is responsible for the sorbance in environment.     

Neptunium(V) adsorption to calcite

The migration behavior of the actinyl ions U(VI)O₂²⁺, Np(V)O₂⁺ and Pu(V,VI)O₂^(+,2+) in the geosphere is to a large extend controlled by sorption reactions (inner- or outer-sphere adsorption, ion-exchange, coprecipitation/structural incorporation) with minerals. Here NpO₂⁺ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0–9.4) and concentration (0.4 μM–40 μM) conditions. pH is adjusted by variation of CO₂ partial pressure. Adsorption is found to be pH dependent with maximal adsorption at pH 8.3 decreasing with increasing and decreasing pH. pH dependence of adsorption decreases with increasing Np(V) concentration. EXAFS data of neptunyl adsorbed to calcite and neptunyl in the supernatant shows differences in the Np(V)-O-yl distance, 1.85 ± 0.01 Å for the adsorbed and 1.82 ± 0.01 Å for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45 ± 0.02 Å. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46 ± 0.01 Å. An additional feature in the adsorbed species' R-space spectrum can be related to carbonate neighbours, 3 to 6 carbon backscatterers (C-eq) at 3.05 ± 0.03 Å and 3 to 6 oxygen backscatterers (O-eq2) at 3.31 ± 0.02 Å. The differences in the Np(V)-O-yl distance and the C-eq and O-eq2 backscatterers which are only present for the adsorbed species indicate inner-sphere bonding of the adsorbed neptunyl species to the calcite surface. Experiments on adsorption kinetics indicate that after a fast surface adsorption process a continuous slow uptake occurs which may be explained by incorporation via surface dissolution and reprecipitation processes. This is also indicated by the part irreversibility of the adsorption as shown by increased K_D values after desorption compared to adsorption.