Impact of major organophosphate pesticides used in agriculture to surface water and sediment quality (Southern Caspian Sea basin,Haraz River)

Organophosphate pesticides are compounds that are not only toxic to both humans and wildlife but also difficult to degrade under natural environmental conditions. In Iran, agricultural practices are strongly dependent on the use of pesticides due to climatic and soil conditions, thus posing a potential risk to groundwater quality standards. Evaluating the concentration of organophosphate pesticides namely diazinon, fenitrothion, dichlorvos, ethion, profenofos, malathion and azinphos methyl in water samples in May (low precipitation rate), December (high precipitation rate) as well as the concentration in sediments along the Haraz River is taken into consideration in this study. Generally the pesticides concentration in water samples are relatively higher in May in comparison with that in December; this fact may be due to two major reasons: the first reason is attributed to the prompt raining after the treatment period of most orchards and dry farming lands that will terminate in more wash out of such pesticides towards the branches and main river channel, while the second reason may be considered as the less river water dilution rate in May because of lower precipitation rate. Furthermore, the relatively higher concentrations in downstream stations may be contributed to more intensified agricultural (specially rice paddies), urban and rural land uses in this region in comparison with upstream areas which contain mainly dry farming, grazing lands and orchards with relatively lower loads of pesticides. Additionally, as the Henry’s law constant of all pesticides considered in this study are relatively low, volatilization may not be regarded as an important route of dissipation. Diazinon, azinphos methyl and dichlorvos showed the highest water concentrations in comparison with other pesticides that may be justified by their extended use within the basin during last decades. Based on the chemical properties as well as remarkably higher values in sediment samples in comparison with water ones, it is concluded that the two pesticides, ethion and fenitrothion, persist in the environment due to non-degradable tendencies. Although the concentration of mentioned pesticides is not so high in the water samples, more precautions must be considered in their future use. Regarding the sorption coefficient variation alongside the river, the higher values in upstream and central parts may be attributed to the higher potential of different types of erosion regarding deeper slopes and also sand, gravel and carbonate mining activities at the banks and also river bed in such regions which is considered as an anthropogenic disturbance. In case of central parts, in addition to mentioned reasons, the existence of coal outcrops in the geologic texture of the study area may also be considered as a key role in augmentation of the sorption coefficient. Finally, the dominant clayey and loamy soils containing more organics may be attributed as the major reason of sorption tendency in downstream.     

Chemical changes in fluid composition due to CO2 injection in the Altmark gas field: preliminary results from batch experiments

Dissolution?Cprecipitation phenomena induced by CO₂ injection to Altmark Permian sandstone were observed through laboratory experiments carried out under simulated reservoir conditions (125?°C and 50 bars of pressure). The rock sample was collected from the Altmark gas reservoir, which is being considered for enhanced gas recovery. Two sets of experiments were performed with pulverized rock samples in a closed batch reactor with either pure water (run 1) or 3?M aqueous NaCl solution (run 2) and reacted with injected CO₂ for 3, 5, and 9?days. The liquid samples were analyzed by inductively coupled plasma optical emission spectroscopy and total reflection X-ray fluorescence, where the latter proved to be a feasible alternative to conventional analytical techniques, especially since only small sample volumes (about 10???l) are needed. Chemical analysis for both fluids (water and NaCl brine) indicated a significant dissolution of calcite and anhydrite in the solution, which might be a crucial process during CO₂ injection. The brine solution enhanced the dissolution of calcite and anhydrite compared to pure water at the beginning of the reaction. Moreover, the progressive higher Si⁴⁺/Al³⁺ molar ratios (in average by a factor of 3) in the brine experiments indicated quartz dissolution. Thermodynamic calculations of mineral saturation indices highlighted the dissolution of the Ca-bearing minerals, which was in agreement with experimental results. Modeling enabled an evaluation of the dissolution processes of minerals in a low-salinity region, yet hindrances to model more saline conditions emphasize the need for further laboratory studies in order to parameterize models for deep aquifer conditions.     

Effect of injected CO2 on geochemical alteration of the Altmark gas reservoir in Germany

Capturing CO₂ from point sources and storing it in geologic formations is a potential option for allaying the CO₂ level in the atmosphere. In order to evaluate the effect of geological storage of CO₂ on rock-water interaction, batch experiments were performed on sandstone samples taken from the Altmark reservoir, Germany, under in situ conditions of 125 °C and 50 bar CO₂ partial pressure. Two sets of experiments were performed on pulverized sample material placed inside a closed batch reactor in (a) CO₂ saturated and (b) CO₂ free environment for 5, 9 and 14 days. A 3M NaCl brine was used in both cases to mimic the reservoir formation water. For the “CO₂ free” environment, Ar was used as a pressure medium. The sandstone was mainly composed of quartz, feldspars, anhydrite, calcite, illite and chlorite minerals. Chemical analyses of the liquid phase suggested dissolution of both calcite and anhydrite in both cases. However, dissolution of calcite was more pronounced in the presence of CO₂. In addition, the presence of CO₂ enhanced dissolution of feldspar minerals. Solid phase analysis by X-ray diffraction and Mössbauer spectroscopy did not show any secondary mineral precipitation. Moreover, Mössbauer analysis did not show any evidence of significant changes in redox conditions. Calculations of total dissolved solids’ concentrations indicated that the extent of mineral dissolution was enhanced by a factor of approximately 1.5 during the injection of CO₂, which might improve the injectivity and storage capacity of the targeted reservoir. The experimental data provide a basis for numerical simulations to evaluate the effect of injected CO₂ on long-term geochemical alteration at reservoir scale.     

Nitrate reduction potential of a fractured Middle Triassic carbonate aquifer in Southwest Germany

Hydrogeology Journal - Nitrate reduction constitutes an important natural mechanism to mitigate the widespread and persistent nitrate contamination of groundwater resources. In fractured aquifers,...     

http://www.sciencedirect.com/science/article/pii/S1674987112000424

Subcooled liquid solubility is the water solubility for a hypothetical state of liquid.It is an important parameter for multicomponent nonaqueous phase liquids(NAPLs) containing polycyclic aromatic hydrocarbons(PAHs),which can exist as liquids even though most of the solutes are solid in their pure form at ambient temperature.So far,subcooled liquid solubilities were estimated from the solid water solubility and fugacity ratio of the solid and(subcooled) liquid phase,but rarely derived from experimental data.In our study,partitioning batch experiments were performed to determine the subcooled liquid solubility of PAHs in NAPL-water system.For selected PAH,a series of batch experiments were carried out at increased mole fractions of the target component in the NAPL and at a constant NAPL/ water volume ratio.The equilibrium aqueous PAH concentrations were measured with HPLC and/or GCMS. The subcooled liquid solubility was derived by extrapolation of the experimental equilibrium aqueous concentration to a mole fraction of unity.With the derived subcooled liquid solubility,the fugacity ratio and enthalpy of fusion of the solute were also estimated.Our results show a good agreement between the experimentally determined and published data.     

Indications for pedogenic formation of perylene in a terrestrial soil profile: Depth distribution and first results from stable carbon isotope ratios

Concentrations and isotope compositions of polycyclic aromatic hydrocarbons (PAHs) were determined in natural soils of Southern Germany. In selected profiles perylene concentrations increased with soil depth when compared to the other PAH compounds present. However, its low solubility made vertical transport by seepage water unlikely. Therefore two mechanisms are discussed that could have caused the unusual distribution of perylene in these soils:

(a) Atmospheric deposition of combustion-derived (i.e. pyrogenic) perylene in the top-soil and

(b) in situ generation in the sub-soil of these specific terrestrial environments. This could have been caused by microbial activities or other catalytic processes yet unknown.

In order to distinguish between pyrogenic and natural generation compound-specific ¹³C/¹²C ratios (δ¹³C) were compared between perylene and other PAHs in samples from the top-soil and sub-soil. Despite successful clean-up of the extracts, low perylene concentrations and peak overlaps with benzo(e)pyrene and benzo(a)pyrene prevented determination of a unique δ¹³C value for perylene in the upper horizon. However, the δ¹³C value of perylene in the sub-soil was 5.7 permille more negative than other equal-mass PAHs (with m/z of 252) in the top-soil, which rather supports in situ generation of perylene in the sub-soil.     

Experimental Sensitivity Analysis of Oxygen Transfer in the Capillary Fringe

Oxygen transfer in the capillary fringe (CF) is of primary importance for a wide variety of biogeochemical processes occurring in shallow groundwater systems. In case of a fluctuating groundwater table two distinct mechanisms of oxygen transfer within the capillary zone can be identified: vertical predominantly diffusive mass flux of oxygen, and mass transfer between entrapped gas and groundwater. In this study, we perform a systematic experimental sensitivity analysis in order to assess the influence of different parameters on oxygen transfer from entrapped air within the CF to underlying anoxic groundwater. We carry out quasi two‐dimensional flow‐through experiments focusing on the transient phase following imbibition to investigate the influence of the horizontal flow velocity, the average grain diameter of the porous medium, as well as the magnitude and the speed of the water table rise. We present a numerical flow and transport model that quantitatively represents the main mechanisms governing oxygen transfer. Assuming local equilibrium between the aqueous and the gaseous phase, the partitioning process from entrapped air can be satisfactorily simulated. The different experiments are monitored by measuring vertical oxygen concentration profiles at high spatial resolution with a noninvasive optode technique as well as by determining oxygen fluxes at the outlet of the flow‐through chamber. The results show that all parameters investigated have a significant effect and determine different amounts of oxygen transferred to the oxygen‐depleted groundwater. Particularly relevant are the magnitude of the water table rise and the grain size of the porous medium.     

Groundwater temperature evolution in the subsurface urban heat island of Cologne,Germany

Long‐term heating of shallow urban aquifers is observed worldwide. Our measurements in the city of Cologne, Germany revealed that the groundwater temperatures found in the city centre are more than 5 K higher than the undisturbed background. To explore the role of groundwater flow for the development of subsurface urban heat islands, a numerical flow and heat transport model is set up, which describes the hydraulic conditions of Cologne and simulates the transient evolution of thermal anomalies in the urban ground. A main focus is on the influence of horizontal groundwater flow, groundwater recharge and trends in local ground warming. To examine heat transport in groundwater, a scenario consisting of a local hot spot with a length of 1 km of long‐term ground heating was set up in the centre of the city. Groundwater temperature‐depth profiles at upstream, central and downstream locations of this hot spot are inspected. The simulation results indicate that the main thermal transport mechanisms are long‐term vertical conductive heat input, horizontal advection and transverse dispersion. Groundwater recharge rates in the city are low (<100 mm a^?1) and thus do not significantly contribute to heat transport into the urban aquifer. With groundwater flow, local vertical temperature profiles become very complex and are hard to interpret, if local flow conditions and heat sources are not thoroughly known. Copyright © 2014 John Wiley & Sons, Ltd.