Predicting the impact and duration of persistent and mobile organic compounds in groundwater systems using a contaminant mass discharge approach.

This study investigated methods for predicting the duration and impact on groundwater quality from persistent and mobile organic compounds (PMOCs) at a drinking water well field affected by multiple contaminant sources. The fungicide metabolite N,N-dimethylsulfamide (DMS), which frequently occurs above the Danish groundwater quality criterion (0.1 µg/L), was used as an example. By combining contaminant mass discharge (CMD) estimations, modeling, and groundwater dating, a number of important discoveries were made. The current center of contaminant mass was located near the source area. The CMD at the well field was predicted to peak in 2040, and an effect from the investigated sources on groundwater quality could be expected until the end of the 21st century. A discrepancy in the current CMD at the well field and the estimated arrival time from the studied source area suggested an additional pesticide source, which has not yet been thoroughly investigated. The presence of the unknown source was supported by model simulations, producing an improved mass balance after inclusion of a contaminant source closer to the well field. The approach applied here was capable of predicting the duration and impact of DMS contamination at a well field at catchment scale. It furthermore shows potential for identification and quantification of the contribution from individual sources, and is also applicable for other PMOCs. Predicting the duration of the release and impact of contaminant sources on abstraction wells is highly valuable for water resources management and authorities responsible for contaminant risk assessment, remediation, and long-term planning at water utilities.

Long-term leaching through clayey till of N,N-dimethylsulfamide, a Persistent and Mobile Organic Compound (PMOC).

Environmental pollution with Persistent and Mobile Organic Compounds (PMOC) from anthropogenic activities is an increasing cause for concern. These compounds are readily leached to groundwater aquifers and are likely to resist degradation, putting pressure on groundwater resources. Pesticides can form PMOCs upon degradation in the environment. The PMOC N,N-dimethylsulfamide (DMS) was the most frequently detected pesticide metabolite in Danish drinking water wells in 2020, although the pesticidal use of the last parent compound (tolylfluanid) ended in 2007. This study aimed to improve the understanding of the leaching of the PMOC DMS from clayey tills by combining a review of compound properties, sources and use, comprehensive field observations and numerical flow and solute transport modeling. The modeling explored the mechanisms of DMS retention during vertical transport in clayey till and the fingerprint in the underlying aquifer. The results were supported by detailed field observations at an agricultural site with strawberry production. Porewater samples were collected from clayey till to a depth of 12 m bgs by a custom designed installation method of suction cups. Groundwater sampling (249 samples) was designed to provide vertical concentration profiles at various distances from the presumed sources. The review of properties showed that the parent compounds and intermediates degrade quickly in topsoil, releasing the highly persistent and mobile DMS. We tested the effect of fractures on transport with different hydraulic apertures and a scenario without fractures by numerical modeling. The results showed that the presence of fractures can smooth the breakthrough curve below the clayey till, leading to faster breakthrough, lower maximum concentration, and several decades of prolonged leaching in simulations with the largest aperture (20 µm). The fracture-matrix interaction is a possible explanation for the observed delay of leaching from clayey till. The vertical concentration profiles in groundwater were used for identifying the sources at the field site and testing source strengths. Assigning one point source (200 µg/L) and two diffuse sources (40-50 µg/L) to the model produced vertical concentration profiles that compared well with observed field data in clayey till and the aquifer. All results were integrated into a conceptual model for the environmental fate of PMOCs in soil and groundwater. The findings of this study imply that the presence of fractures in clayey till should be considered in conceptual site models, since they can substantially prolong the leaching of PMOCs to groundwater. The integration of comprehensive field investigations and numerical modeling is key to understand the fate of PMOCs in complex field systems with different source types. Together with widespread occurrences of PMOCs in groundwater systems, the results highlight the need for improved approval procedures for pesticides and biocides which considers their persistent and mobile metabolites.

Multitechnique Determination of Halogens in Soil after Selective Volatilization Using Microwave-Induced Combustion.

A method for digestion of soils with high inorganic matter content (ranging from 50 to 92%) by microwave-induced combustion (MIC) is proposed for the first time for further halogens (F, Cl, Br, and I) determination by ion chromatography (IC) and also by inductively coupled plasma mass spectrometry (ICP-MS). Microcrystalline cellulose (100-500 mg), used as a combustion aid, was mixed with sample and water or NH4OH solutions (10-100 mmol L-1) were investigated for analytes absorption. The use of cellulose (400 mg) was mandatory to volatilize the halogens from soils with high inorganic matter. It was possible to use diluted absorbing solutions (up to 100 mmol L-1 NH4OH) for halogens retention, providing limits of quantification in the range of 0.06 (I) to 60 (Cl) µg g-1. Accuracy was evaluated using certified reference materials (CRMs), spiked samples, and pyrohydrolysis method. Recoveries for halogens after spiked samples were in the range of 94 to 103% and the results after digestion of CRMs by MIC were in agreement better than 95% to certified values. Blanks were low, relative standard deviation was below 8% for all soils and no statistical difference was observed for results by pyrohydrolysis and MIC methods showing the feasibility of the proposed method for further halogens determination in soil samples.

Purification and structural analysis of a type III antifreeze protein from the european eelpout Zoarces viviparus.

It has recently been reported that the eelpout Zoarces viviparus synthesizes a family of antifreeze proteins (AFP) similar in sequence to type III AFPs. A method has been set up to separate these antifreeze proteins from blood serum of this teleost species. A total of nine proteins with antifreeze activity have been isolated, several to a purity suited for NMR experiments. One of the proteins, Zvafp13, has been subject to partial structure determination by NMR. 1D- and 2D-H NMR analyses were carried out. In the 1D-experiments it was observed that the protein contained 28 slow-exchanging amides, suggesting a compact structure. The 2D-experiments were utilized to assign observed signals to specific amino acids. From TOCSY- and NOESY-experiments 35 out of a total of 66 amino acids were assigned. The amide exchange pattern, protein primary sequence, chemical shifts and NOE-cross-peaks between amides and -protons in the -sheets suggest that Zvafp13 structurally resembles the recombinant type III AFP rQAE m1.1.