Gry Sander Janniche

Microbial Community-Level Physiological Profiles (CLPP) and herbicide mineralization potential in groundwater affected by agricultural land use

Diffuse groundwater pollution from agricultural land use may impact the microbial groundwater community, which was investigated as Community-Level Physiological Profiles (CLPP) using EcoPlate™. Water was sampled from seven piezometers and a spring in a small agricultural catchment with diffuse herbicide and nitrate pollution. Based on the Shannon-Wiener and Simpsons diversity indices the diversity in the microbial communities was high. The response from the EcoPlates™ showed which substrates support groundwater bacteria, and all 31 carbon sources were utilized by organisms from at least one water sample. However, only nine carbon sources were utilized by all water samples: d-Mannitol, N-acetyl-d-glucosamine, putrescine, d-galacturonic acid, itaconic acid, 4-hydroxy benzoic acid, tween 40, tween 80, and l-asparagine. In all water samples the microorganisms preferred d-mannitol, d-galacturonic acid, tween 40, and 4-hydroxy benzoic acid as substrates, whereas none preferred 2-hydroxy benzoic acid, α-d-lactose, d,l-α-glycerol phosphate, α-ketobutyric acid, l-threonine and glycyl-l-glutamic acid. Principal Component Analysis of the CLPPs clustered the most agriculturally affected groundwater samples, indicating that the agricultural land use affects the groundwater microbial communities. Furthermore, the ability to mineralize atrazine and isoproturon, which have been used in the catchment, was also associated with this cluster.

Vertical small scale variations of sorption and mineralization of three herbicides in subsurface limestone and sandy aquifer.

Vertical variation in sorption and mineralization potential of mecoprop (MCPP), isoproturon and acetochlor were investigated at low concentrations (μg-range) at the cm-scale in unsaturated sub-surface limestone samples and saturated sandy aquifer samples from an agricultural catchment in Brévilles, France. From two intact core drills, four heterogenic limestone sections were collected from 4.50 to 26.40m below surface (mbs) and divided into 12 sub-samples of 8-25cm length, and one sandy aquifer section from 19.20 to 19.53m depth divided into 7 sub-samples of 4-5cm length. In the sandy aquifer section acetochlor and isoproturon sorption increased substantially with depth; in average 78% (acetochlor) and 61% (isoproturon) per 5cm. Also the number of acetochlor and isoproturon degraders (most-probable-number) was higher in the bottom half of the aquifer section (93->16000/g) than in the upper half (4-71/g). One 50cm long limestone section with a distinct shift in color showed a clear shift in mineralization, number of degraders and sorption: In the two brown, uppermost samples, up to 31% mecoprop and up to 9% isoproturon was mineralized during 231 days, the numbers of mecoprop and isoproturon degraders were 1300 to >16000/g, and the sorption of both isoproturon and acetochlor was more than three times higher, compared to the two deeper, grayish samples just below where mineralization (≤4%) and numbers of degraders (1-520/g) were low for all three herbicides. In both unsaturated limestone and sandy aquifer, variations and even distinct shifts in both mineralization, number of specific degraders and sorption were seen within just 4-15cm of vertical distance. A simple conceptual model of herbicides leaching to groundwater through a 10m unsaturated limestone was established, and calculations showed that a 30cm active layer with the measured sorption and mineralization values hardly impacted the fate of the investigated herbicides, whereas a total thickness of layers of 1m would substantially increase natural attenuation.

Acetochlor sorption and degradation in limestone subsurface and aquifers

BACKGROUND Acetochlor, introduced on the market in 1994, is used extensively worldwide, but sorption and degradation studies, including subsurface, are scarce, and there appear to be no such studies with aquifer sediment according to the present mini-review. Sorption, degradation and mineralisation of acetochlor were investigated in heterogeneous limestone down to 43 m below surface (mbs) in four European aquifers (1.7-59 mbs), both aerobic and anaerobic. RESULTS Sorption revealed K(d) values of 3.39-4.96 L kg(-1) in topsoil, < 0.01-2.02 L kg(-1) in heterogeneous limestone, 0.06-0.72 L kg(-1) in aerobic aquifers and 1.03-4.60 L kg(-1) in microaerobic or anaerobic aquifers. The mineralisation half-lives in the samples from 0.0-0.6 mbs were 0.8-2.1 years and 4.7-95 years in the unsaturated limestone samples from 1-43 mbs. Out of 22 samples from four different European aquifers, acetochlor was mineralised in five samples (half-lives of 9-19 years), all from the same aquifer and core section (19.25-19.53 mbs). CONCLUSION Sorption was weak in limestone and aerobic sandy aquifers, and strong in topsoils and in reduced sandy aquifers. Redox conditions controlled the extent of acetochlor sorption in aquifers, as reduced conditions induced increased sorption. Acetochlor was mineralised in deep subsurface, though slowly, and, as mineralisation is the only true removal mechanism in natural attenuation, even slow mineralisation in aquifers with long residence times can have a significant impact.

Inherent mineralization of 2,6-dichlorobenzamide (BAM) in unsaturated zone and aquifers – Effect of initial concentrations and adaptation

The dichlobenil metabolite BAM (2,6-dichlorobenzamide) is frequently detected in aquifers e.g. in Denmark despite the mother compound dichlobenil was banned here since 1997. BAM mineralization was investigated at environmentally relevant concentrations in sediment samples. Undisturbed sediment cores with known dichlobenil application were collected from topsoil to 8.5 m below surface resulting in 57 samples hereof 4 aquifer samples. Mineralization was only substantial (>10%) in the uppermost meter of the unsaturated zone. Microbial adaptation, observed as faster mineralization in pre-exposed than in pristine sediments from the same location, was only evident in sandy sediment where dichlobenil was still present, but not in clayey sediments. Higher initial concentrations (1-5000 μg/kg) did not stimulate mineralization in pristine clayey or sandy sediments, or in pre-exposed sand. However, in pre-exposed clay mineralization was stimulated at high concentrations. Furthermore BAM was for the first time mineralized in aerobic aquifer sediments from different BAM-contaminated groundwater locations.

Characterization of chlorinated solvent contamination in limestone using innovative FLUTe® technologies in combination with other methods in a line of evidence approach.

Characterization of dense non-aqueous phase liquid (DNAPL) source zones in limestone aquifers/bedrock is essential to develop accurate site-specific conceptual models and perform risk assessment. Here innovative field methods were combined to improve determination of source zone architecture, hydrogeology and contaminant distribution. The FACT™ is a new technology and it was applied and tested at a contaminated site with a limestone aquifer, together with a number of existing methods including wire-line coring with core subsampling, FLUTe® transmissivity profiling and multilevel water sampling. Laboratory sorption studies were combined with a model of contaminant uptake on the FACT™ for data interpretation. Limestone aquifers were found particularly difficult to sample with existing methods because of core loss, particularly from soft zones in contact with chert beds. Water FLUTe™ multilevel groundwater sampling (under two flow conditions) and FACT™ sampling and analysis combined with FLUTe® transmissivity profiling and modeling were used to provide a line of evidence for the presence of DNAPL, dissolved and sorbed phase contamination in the limestone fractures and matrix. The combined methods were able to provide detailed vertical profiles of DNAPL and contaminant distributions, water flows and fracture zones in the aquifer and are therefore a powerful tool for site investigation. For the limestone aquifer the results indicate horizontal spreading in the upper crushed zone, vertical migration through fractures in the bryozoan limestone down to about 16-18m depth with some horizontal migrations along horizontal fractures within the limestone. Documentation of the DNAPL source in the limestone aquifer was significantly improved by the use of FACT™ and Water FLUTe™ data.