Sorption of tetracycline to sediments and soils: assessing the roles of pH,the presence of cadmium and properties of sediments and soils

Batch sorption experiments were conducted to evaluate the sorption behavior of tetracycline (TC, H₃L) on sediments and soils in the presence and absence of cadmium (Cd), as affected by pH and properties of sediments and soils. The results indicated stronger nonlinearity and higher capacity of TC sorption on sediments than on soils. Sorption of TC also strongly depended on environmental factors and sediment/soil properties. Lower pH facilitated TC sorption through a cation exchange mechanism, which also took place at pH values above 5.5, where TC existed as a zwitterion (H₂L⁰) or anions (HL^- and L^2-). When pH was above 7, however, ligand-promoted dissolution of TC might occur due to TC weakening the Al-O bond of aluminum oxide and the Fe-O bond of iron oxide. Natural organic matter (NOM) plays a more important role in TC sorption than cation exchange capacity (CEC) and clay contents. The presence of Cd (II) increased TC sorption on both sediments and soils, which resulted from the decrease of equilibrium solution pH caused by Cd²⁺ exchange with H⁺ ions of sediment/soil surfaces. The increase of TC sorption was also related to the formation of TC-Cd complexes, where Cd²⁺ acted as a bridge between the sediment/soil and TC.     

Removal of high concentrations of polycyclic aromatic hydrocarbons from contaminated soil by biodiesel

Solubilizing experiments were carried out to evaluate the ability of biodiesel to remove polycyclic aromatic hydrocarbons (PAHs) from highly contaminated manufactured gas plant (MGP) and PAHs spiked soils with hydroxypropyl-β-cyclodextrin (HPCD) and tween 80 as comparisons. Biodiesel displayed the highest solubilities of phenanthrene (420.7 mg·L^-1), pyrene (541.0 mg·L^-1), and benzo(a)pyrene (436.3 mg·L^-1). These corresponded to several fold increases relative to 10% HPCD and tween 80. Biodiesel showed a good efficiency for PAH removal from the spiked and MGP soils for both low molecular weight and high molecular weight PAHs at high concentrations. Biodiesel was the best agent for PAH removal from the spiked soils as compared with HPCD and tween 80; as over 77.9% of individual PAH were removed by biodiesel. Tween 80 also showed comparable capability with biodiesel for PAH solubilization at a concentration of 10% for the spiked soils. Biodiesel solubilized a wider range of PAHs as compared to HPCD and tween 80 for the MPG soils. At PAH concentrations of 229.6 and 996.9 mg·kg^-1, biodiesel showed obvious advantage over the 10% HPCD and tween 80, because it removed higher than 80% of total PAH. In this study, a significant difference between PAH removals from the spiked and field MGP soils was observed; PAH removals from the MGP soil by HPCD and tween 80 were much lower than those from the spiked soil. These results demonstrate that the potential for utilizing biodiesel for remediation of highly PAH-contaminated soil has been established.     

Beurteilung des Ozonrisikos für die Waldregionen Bayerns am Beispiel des Jahres 2002 und des Extremtrockenjahres 2003 auf der Basis der externen Ozonexposition und der internen Ozonaufnahme

Background, aim, and scope Increasing background concentrations of ground-level tropospheric ozone and more frequent and prolonged summer drought incidences due to climate change are supposed to increase the stress on Bavarian forests. For such scenarios growth reduction and yield losses are predicted. Sustainable forest management in Bavaria aims to significantly increase the proportion of beech (Fagus sylvatica L.) because of its broad ecological amplitude. In our regional study different approaches for calculating ozone impact were used to estimate the risks for Bavarian forests in the average climatic, rather moist year 2002 and the extremely dry year 2003.Materials and methods Measurements were conducted for eleven forest ecosystem sites and two forest research sites representing typical Bavarian forest stands under different climatic conditions and situated in different altitudes. For risk assessment currently used approaches were applied either based on the calculation of the cumulative ozone exposure (external dose; MPOC maximal permitted ozone concentration; critical level AOT40_phen? accumulated ozone exposure over a threshold of 40 nl [O₃] l^–1, for the effective phenolgy of beech) or based on the calculation of the phytomedically relevant ozone flux into the stomata (internal dose, critical level AF_st>1,6, accumulated stomatal flux above a flux threshold of 1.6 nmol O₃?m^–2 PLA; PLA = projected leaf area). For calculations continuously recorded ozone concentrations and meteorological and phenological data from nearby rural open field background measuring stations from the national air pollution control and from forested sites were used. Additionally ozone induced leaf symptoms were assessed.Results The exposure-based indices AOT40_phen and MPOC as well as the flux-based index AF_st>1.6suggest that Bavarian forests are at risk from O₃ during a rather moist average year concerning climate conditions (2002) as well as in an extreme dry year (2003). Thus, growth reductions of 5?% are predicted when thresholds are exceeded. Threshold exceedance occurred in both years at all plots, mostly already at the beginning of the growing season and often even many times over. Ozone induced leaf symptoms could be detected only on a few plots in a very slight occurrence.Discussion The results for the applied critical level indices differed depending on climatic conditions during the growing seasons: Regarding exposure-based indices, the highest degree of threshold exceedance occurred in the dry year of 2003 at all plots; the flux-based approach indicated the highest stomatal ozone uptake and thus an increased risk at moist sites or during humid years, whereas the risk was decreasing at dry sites with prolonged water limitation. Hence, soil and accordingly plant water availability was the decisive factor for the flux-modelled internal ozone uptake via stomata. Drought and increased ozone impact can generate synergistic, but also antagonistic effects for forest trees. At water limited rather dry forest sites restricted transpiration and thus production, but concurrently lower ozone uptake and reduced risk for damage can be expected.Conclusions, recommendations, and perspectives For realistic site-specific risk assessment in forest stands the determination of the internal ozone dose via modeling flux based internal stomatal ozone uptake is more appropriate than the calculation of the external ozone dose. The predicted 5?% growth reductions are in discrepancy with the frequently observed increment increase during the last decades in forest stands. Comprehensive and significant statistical verification for ozone induced forest growth reduction as well as the systematic validation of thresholds for ozone in the field is still lacking. However, a multiplicity of different specific new and retrospective growth analysis data should allow closing the gap. Moreover, the determination of canopy transpiration with sap flow measurements is a novel approach to provide cause-effect related, site specific results for the effective internal ozone dose as well as for canopy water supply and consecutively for regional risk estimation. A further future objective is the refinement of O₃ flux modelling by further consideration of soil/water budget characteristics and the above mentioned improved estimations of crown and canopy transpiration. Further, the introduction of threshold ranges for forest trees in view of their specific regional climatic conditions and their validation in real forest stands is necessary for developing meaningful ozone risk predictions for forests.     

Environmental impact of historical harbour city Zadar (Croatia) on the composition of marine sediments and soils

Sediment samples and soils along the coast line of the Adriatic Sea were sampled along a transect near the coast line at Zadar/Croatia, ranging from north-western suburbs via the historical centre and the industrial area to south-east suburbs. The sediments were dominated by carbonates and clay minerals, and contaminations with Cd–Cu–Pb–Zn–TOC (total organic carbon) at the historical centre and the industrial site were detected, as well as P and Mo input at the mouth of a small creek, probably from agriculture. No trends between the composition of surface and subsurface sea sediments were seen. At the historic harbour site, total element concentrations versus grain size showed a minimum in the fine silt fraction for most of the elements analysed. The soil samples behind the shoreline were not carbonaceous, but dominated by Fe–Al– oxides, some contained high levels of Be–Cd–Cu–Sn–Zn. Surprisingly, high TOC values within the soils might be assigned to human impacts, not to humus. Contrary to data from street dust samples from Seoul city/Korea, which were measured within our laboratory at the same time, Pt–Ir–Au were at ambient levels due to the limited use of catalysts in cars in the Zadar area at the time of sampling.     

The role of black carbon as a catalyst for environmental redox transformation

Black carbon (BC) is an important class of geosorbents that control the fate and transport of organic pollutants in soil and sediment. We previously demonstrated a new role of BC as an electron transfer mediator in the abiotic reduction of nitroaromatic and nitramine compounds by Oh and Chiu (Environ Sci Technol 43:6983–6988, 2009). We proposed that BC can catalyze the reduction of nitro compounds because it contains microscopic graphitic (graphene) domains, which facilitate both sorption and electron transfer. In this study, we assessed the ability of different types of BC—graphite, activated carbon, and diesel soot—to mediate the reduction of 2,4-dinitrotoluene (DNT) and 2,4-dibromophenol (DBP) by H₂S. All three types of BC enhanced DNT and DBP reduction. H₂S supported BC-mediated reduction, as was observed previously with a thiol reductant. The results suggest that BC may influence the fate of organic pollutants in reducing subsurface environments through redox transformation in addition to sorption.     

Distributional patterns of adult male loggerhead sea turtles (<Emphasis Type="Italic">Caretta caretta</Emphasis>) in the vicinity of Cape Canaveral,Florida, USA during and after a major annual breeding aggregation

Satellite transmitters were attached to 25 reproductively active and four inactive adult male loggerhead sea turtles (86.6–107.0 cm SCLmin) captured from the Port Canaveral, FL, USA shipping channel to assess horizontal and vertical distributions. During the breeding period, male loggerheads aggregated (44% of 755 turtle days) in a 117.6 km² core area that encompassed the shipping channel. Median dive duration during the breeding period was 27 min (IQR = 15–42 min) and males spent 4% (IQR = 3–5%) of the time at the surface, with significantly shorter dives associated with reproductively active males. Migrant and resident males dispersed concurrently, with residents shifting > 30 km east across the continental shelf over a more protracted departure schedule than migrants. Dive duration and time spent at the surface increased through the fall. Cluster analysis revealed the strongest association for dive duration with sea state during and after the breeding period, with significantly longer dives during more turbulent conditions. In contrast, univariate associations with surface interval duration were not elucidated.     

Trade-off between pre- and postcopulatory sexual cannibalism in a wolf spider (Araneae,Lycosidae)

Sexual cannibalism can occur before, during or after mating. Relatively few experimental studies have examined why there is variation in the timing of sexual cannibalism. We examined the latency and number of attacks required for female spiders to capture male spiders pre- vs. postcopulation. We also examined the effects of female mating status and hunger level on the occurrence of pre- and postcopulatory cannibalism, which reflects the contribution of both relative capture success and female motivation to cannibalize males. Precopulatory cannibalism occurred after a shorter interval and required fewer chases and physical interactions for the female to successfully capture the male than was the case for postcopulatory cannibalism. Virgin females were more likely to engage in postcopulatory rather than precopulatory cannibalism and mated females vice versa. Those virgin females that did engage in precopulatory cannibalism had significantly lower body condition than virgin females engaging in postcopulatory cannibalism. While precopulatory cannibalism occurred more quickly and required fewer attacks by females, it comes at a potential cost of not mating with males. Hence, females are more likely to engage in precopulatory cannibalism if they have already mated or, if virgins, if they have low body condition. These results indicate that the decision of when to cannibalize males is dynamic and depends upon the relative value of a male as a mate versus a meal.     

Genetic mating system of the brown smoothhound shark (<Emphasis Type="Italic">Mustelus henlei</Emphasis>), including a literature review of multiple paternity in other elasmobranch species

Although an understanding of mating systems is thought to be an important component of long-term population management, these life history characteristics are poorly known in sharks. Here, we employ polymorphic microsatellite markers to test for the occurrence and prevalence of multiple paternity in a population of the brown smoothhound shark, Mustelus henlei. We analyzed litters from 14 females sampled from the Pacific coast of Baja California Sur. The minimum number of sires ranged from one to three with an average of 2.3 sires per litter. Regression analyses did not indicate a relationship between female body size and number of sires, or female body size and size of the litter. A review of the existing literature on genetic mating systems in sharks suggests that polyandry may be common and that reproductive behavior may have evolved from conflicting selection pressures between the sexes.     

Stable isotope ratios of a tropical marine predator: confounding effects of nutritional status during growth

Stable isotope analysis of carbon and nitrogen is frequently used to study the diets and foraging ecology of marine predators. However, isotopic values may also be affected by an individual’s nutritional status and associated physiological processes. Here, we use C and N stable isotopes in blood and feathers of blue-footed booby chicks at the Galápagos Islands to examine how isotopic values are related to body condition and growth rate, and to assess the consistency in the isotope ratios of individuals during growth. Size dimorphism in blue-footed boobies provided an additional opportunity to examine how isotope ratios differ between sexes in relation to body size and growth rate. There was no significant difference between sexes but both C and N stable isotopes were significantly negatively related to the body condition of chicks. These data were consistent with individual variation in physiological processes affecting fractionation, although we cannot rule out the possibility that they were also influenced to some extent by population-level variation in the stable isotope ratios of prey fed to chicks, for instance related to prey size, depth or lipid content. Our results highlight the need for methods that take proper account of confounding physiological factors in isotopic studies of foraging ecology and diet.     

Size-dependent behavior of tuna in an array of fish aggregating devices (FADs)

Several lines of evidence indicate that aggregations of yellowfin tuna associated with floating objects are more frequently composed of small animals than larger ones. Also, the diet of small yellowfin tuna caught at anchored fish aggregating devices (FADs) around Oahu, Hawaii, was found to shift quite rapidly when these fish reached approximately 50 cm FL. In order to test for ontogenetic changes in aggregation behavior, we tagged and released two distinct size classes of yellowfin tuna in an array of anchored FADs around Oahu, Hawaii. Twenty-four yellowfin tuna 30–39 cm FL and 16 yellowfin tuna 63–83 cm FL were tagged with acoustic transmitters and released near anchored FADs equipped with automated acoustic receivers. Fish in the smaller size class stayed about 2.5 times longer at individual FADs than the larger fish (mean 4.05 days vs. 1.65 days) and displayed larger horizontal movements within the array. However, the durations of unassociated phases, residence times in the entire FAD array, percentage of time spent associated with FADs and numbers of movements between FADs did not show any difference between the two size groups. The observed size-dependent behavior is discussed in terms of physiological abilities, diet segregation and anti-predator behavior.