The impact of livestock activities and geochemical processes on groundwater quality of fractured volcanic rock aquifer: Lake Çildir watershed (NE Turkey).

This paper presents the impact of livestock activities and geochemical processes on the water quality of a fractured volcanic rock aquifer in the Lake Çildir watershed, located at the northeastern part of Turkey. The existence of a high livestock population and animal grazing activities in meadow and pasturelands of the watershed during the short summer period poses serious stress on both surface and groundwater resources being the only drinking water supply for the local communities. Therefore, understanding the effect of grazing and livestock breeding activities occurring in the recharge areas of the fractured volcanic rock aquifer is vital to take precautions in order to protect limited water supplies at the watershed and vulnerable lake ecosystem as well. The mean nitrate content of the groundwater was measured at 6.4 ± 6.6 (std. dev) mg/L in the wet (before grazing) period and 7.1 ± 5.9 mg/L in the dry (after grazing) period. Despite low nitrate concentration levels of groundwater, microbial contamination was observed in the spring waters at alarming levels especially after the animal grazing activities. 56%, 26%, and 11% of the groundwater samples showed bacterial contamination in terms of total coliform, fecal coliform, and fecal streptococci contents, respectively, prior to grazing activity, while in pursuit of intense livestock grazing at highland, these microbial indicators have been increased to 92%, 85%, and 77% in the dry period. A significant increase observed in fecal contamination indicates the negative impact of livestock activities on groundwater quality. Al (200-638 µg/L) and Fe (66-218 µg/L) enrichments locally observed in groundwater were related to advanced argillic alteration (kaolinization) and hematization zones in pyroclastic rocks.

Presence of Toxic Heavy Metals in Platelet-Rich Fibrin: a Pilot Study.

Platelet-rich fibrin (PRF) is widely used blood-derived biomaterial which is directly applied to the surgical wounds. Depending on its autologous origin, PRF is thought as a safe material. However, it is not known to what extent the blood-derived toxins can be found in the PRF by considering the systemic exposure rates of the individuals to the toxins. The aim of this pilot study was to test the hypothesis whether PRF contains any blood-origin heavy metals (HMs) and smoking increases their concentrations as an environmental HM source. PRF samples were obtained from systemically healthy 30 non-smoker and 30 smoker volunteers. All liquid and dry fibrin parts of the PRF samples were analyzed in terms of 15 toxic elements using inductively coupled plasma mass spectrometry. All analyzed HMs were detected in all investigated PRF samples within various concentrations in both groups. In addition, significantly high levels of cadmium, arsenic, lead, manganese, nickel, chromium, and vanadium were detected in dry fibrin matrices of PRF samples of smokers comparing with non-smokers (p < 0.05). Only cadmium was at significantly high levels in the liquid part of PRF samples of smokers (p < 0.05). This is the first study evaluating toxic ingredients of PRF. The results revealed that PRF contains various toxic HMs. Additionally, systemic exposure to environmental HM sources such as smoking may significantly increase HM concentrations in PRF. Further studies are required to investigate the transmission potentials of HMs to the applied tissues and biological importance of PRF-origin HMs.

Sorption and transport of trichloroethylene in caliche soil.

Sorption of TCE to the caliche soil exhibited linear isotherm at the high TCE concentrations (Co=122-1300 mg L(-1)) but Freundlich isotherm at the low concentration range (1-122 mg L(-1)). Sorption strength of the carbonate fraction of the soil was about 100-fold lower than the sorption strength of soil organic matter (SOM) in the caliche soil, indicating weak affinity of TCE for the carbonate fraction of the soil. Desorption of TCE from the caliche soil was initially rapid (7.6×10(-4) s(-1)), then continued at a 100-fold slower rate (7.7×10(-6) s(-1)). Predominant calcium carbonate fraction of the soil (96%) was responsible for the fast desorption of TCE while the SOM fraction (0.97%) controlled the rate-limited desorption of TCE. Transport of TCE in the caliche soil was moderately retarded with respect to the water (R=1.75-2.95). Flow interruption tests in the column experiments indicated that the rate-limited desorption of TCE controlled the non-ideal transport of TCE in the soil. Modeling studies showed that both linear and non-linear nonequilibrium transport models provided reasonably good match to the TCE breakthrough curves (r2=0.95-0.98). Non-linear sorption had a negligible impact on both the breakthrough curve shape and the values of sorption kinetics parameters at the high TCE concentration (Co=1300 mg L(-1)). However, rate-limited sorption/desorption processes dominated at this concentration. For the low TCE concentration case (110 mg L(-1)), in addition to the rate-limited sorption/desorption, contribution of the non-linear sorption to the values of sorption kinetics became fairly noticeable.

Adsorption and transport of arsenate in carbonate-rich soils: coupled effects of nonlinear and rate-limited sorption.

The transport and fate of arsenate in carbonate-rich soil under alkaline conditions was investigated with multiple approaches combining batch, sequential extraction and column experiments as well as transport modeling studies. Batch experiments indicated that sorption isotherm was nonlinear over a wide range of concentration (0.1-200 mg L(-1)) examined. As(V) adsorption to the calcareous soil was initially fast but then continued at a slower rate, indicating the potential effect of rate-limited sorption on transport. Column experiments illustrated that transport of As(V) was significantly retarded compared to a non-reactive tracer. The degree of retardation decreased with increasing As(V) concentration. As(V) breakthrough curves exhibited nonideal transport behavior due to the coupled effects of nonlinear and rate-limited sorption on arsenate transport, which is consistent with the results of modeling studies. The contribution of nonlinear sorption to the arsenate retardation was negligible at low concentration but increased with increasing As(V) concentration. Sequential extraction results showed that nonspecifically sorbed (easily exchangeable, outer sphere complexes) fraction of arsenate is dominant with respect to the inner-sphere surface bound complexes of arsenate in the carbonate soil fraction, indicating high bioavailability and transport for arsenate in the carbonate-rich soils of which Fe and Al oxyhydroxide fractions are limited.

Use of cyclodextrin and calcium chloride for enhanced removal of mercury from soil.

The use of solutions containing carboxymethyl-beta-cyclodextrin (CMCD) or CaCl2 for enhancing the removal of Hg from a sandy soil was investigated using batch and column experiments. The retention of Hg appeared to be controlled by specific adsorption reactions, which greatly constrained Hg removal when using water (KNO3 solution) to flush columns packed with contaminated soil. The results showed that the two reagents did enhance the removal of Hg from the soil. For example, 81% and 60% of Hg was recovered after 50 pore volumes of flushing with 50 mM CaCl2 and 2 mM CMCD, respectively, compared to 24% recovery for a 10 mM KNO3 solution. However, significant tailing and delayed recovery of Hg during the elution process occurred in the presence of all reagents, indicating that the removal of Hg from the soil was rate limited.

The influence of substrate and electron acceptor availability on bioactive zone dynamics in porous media.

Two approaches were used to investigate the influence of dissolved oxygen (DO) and substrate availability on the formation and dynamics of "bioactive zones" in a water-saturated porous medium. A bioactive zone is defined as a region where a microbial community is sufficiently active to metabolize bioavailable substrates. In the first approach, microbial activity was characterized by monitoring the spatial and temporal variability of DO and aqueous substrate (salicylate and naphthalene) concentrations during miscible-displacement experiments. In the second approach, microbial activity was monitored using multiple fiber optics emplaced in the porous medium to detect luminescence produced by Pseudomonas putida RB1353, a bioluminescent reporter organism that produces light when salicylate (an intermediate of naphthalene degradation) is present. The results of both approaches show that the location and size of the bioactive zones were influenced by in situ DO and substrate availability. When DO was not a limiting factor (i.e., lower substrate input concentrations), the bioactive zone encompassed the entire column, with the majority of the microbial activity occurring between the inlet and midpoint. However, as the availability of DO became limiting for the higher substrate input experiments, the size of the bioactive zone shrank and was ultimately limited to the proximity of the column inlet.

Biodegradation during contaminant transport in porous media: V. The influence of growth and cell elution on microbial distribution.

This study investigated the interaction between microbial growth and cell elution, and their influence on resultant microbial distribution between the aqueous and solid phases during solute transport in a sandy, low-organic-carbon-content porous medium. Miscible displacement experiments were conducted with salicylate as the model compound, and with different initial conditions (e.g., substrate concentrations and cell densities) to attain various degrees of microbial growth. For each experiment, salicylate and dissolved oxygen concentrations as well as cell densities were monitored in the column effluent. Cell densities were also measured in the porous medium at the beginning and end of each experiment. Total microbial growth was determined in two ways, one based on a cell mass balance for the system and the other based on total amount of salicylate degraded. For conditions yielding a considerable amount of microbial growth, the majority of the biomass was associated with the aqueous phase (68-90%). Conversely, under minimal-growth conditions, most cells (approximately 60-70%) were attached to particle surfaces. Significant cell elution was observed for most conditions, the rate of which increased in the presence of the substrate. The results suggest that the increase in aqueous-phase cells observed for the experiments exhibiting the greatest growth is associated with the production of new cells, and that under appropriate conditions aqueous-phase biomass can contribute significantly to contaminant biodegradation.