Effects of doping amounts of potassium ferricyanide with titanium dioxide and calcination durations on visible-light degradation of pharmaceuticals

Acetaminophen (ACT) is one of the most frequently detected pharmaceuticals in aqueous environments, and treatment of ACT were generally carried out by photocatalytic degradations under high energy UV irradiation. In this study, potassium ferricyanide was utilized as a quadruple-elemental dopant in a TiO₂ photocatalyst in order to enhance its visible-light activity. Two critical parameters (amounts of dopants and durations of calcination) of the synthesis of the photocatalyst by a sol–gel method were systematically evaluated. Crystal structure of the doping TiO₂ was examined by X-ray diffraction while the effects of the two parameters on the photocatalytic activity were elucidated by various characterizations. Increasing the amount of dopant or the duration of calcination red-shifted the UV–vis DRS of the doped TiO₂. The estimated band gap energy of the doped TiO₂ decreased slightly as the amount of dopant increased, but it increased as the duration of calcination increased. The FT-IR yielded characteristic peaks that revealed the effects of the two parameters, whereas the SEM images revealed the morphological evolutions of each effect. The photocatalyst, synthesized at optimum conditions was able to remove 99.1 % acetaminophen with rate constant of 7.9 × 10⁻³ min⁻¹, which was 4.88 times greater than virgin TiO₂. In general, this study not only optimized synthetic conditions of the new visible-light active photocatalyst for ACT degradation but also presented characterizations conducted by SEM, XRD, UV–vis DRS, and FTIR to elucidate the relationship between modified structure and the photocatalytic activity.

Effects of doping amounts of K₃[Fe(CN)₆] and calcunation duration on visible light absorbance of TiO₂ photocatalysts

     

From wetland to farm and back again: phosphorus dynamics of a proposed restoration project

We studied the phosphorus dynamics in a former wetland, which had been converted to a celery farm, and now consists of two shallow, flooded ponds that are being proposed for aquatic habitat restoration. However, like many agricultural areas, this site is plagued by phosphorus legacy issues. Proposed restoration includes hydrologic reconnection of these ponds to its adjacent stream, which are now isolated from one another by an earthen berm, to create a wetland complex. One of the two flooded ponds was partially dredged, whereas the other one has remained undredged. Water column, sediment pore water, and sediment total phosphorus concentrations were significantly greater in the undredged pond compared to the dredged pond, but in both cases phosphorus levels in the water columns (mean TP 929 vs. 133 μg/L in undredged vs. dredged ponds, respectively) would exacerbate downstream water quality issues if hydrologic reconnection occurred without first addressing the phosphorus issue. Sediment isotherm and maximum sorption data indicated that the sediments are close to phosphorus saturation in the undredged pond; simulated dredging of the cores revealed that exposure of deeper sediment layers would increase sorption capacity. Pore water SRP concentrations increased with sediment depth and were significantly greater in the undredged vs. dredged pond at both the 1–4-cm depth (2249 vs. 112 μg/L) and 14–17-cm depth (5506 vs. 222 μg/L). This study provides a framework for other projects that need to balance the competing demands of habitat restoration vs. water quality when restoring wetlands that have been converted to agricultural production.

     

Polybrominated diphenyl ethers (PBDE) in serum: findings from a US cohort of consumers of sport-caught fish

Polybrominated diphenyl ethers (PBDEs) have been used as flame retardants in foams, fabrics and plastics, and are common contaminants of household air and dust and bioaccumulate in wildlife, and are detectable in human tissues and in fish and animal food products. In the Great Lakes Basin sport fish consumption has been demonstrated to be an important source of PCB and DDE exposure. PBDEs are present in the same sport fish but prior to our study the contribution to human PBDE body burdens from Great Lakes sport fish consumption had not been investigated. This study was designed to assess PBDE, PCB and 1,1-bis(4-chlorophenyl)-2,2-dichloroethene (DDE) serum concentrations in an existing cohort of 508 frequent and infrequent consumers of sport-caught fish living in five Great Lake states. BDE congeners 47 and 99 were identified in the majority of blood samples, 98% and 62% respectively. summation operatorPBDE levels were positively associated with age, hours spent outdoors, DDE, summation operatorPCB, years of sportfish consumption, and catfish and shellfish intake, and negatively associated with income and recent weight loss. Other dietary components collected were not predictive of measured summation operatorPBDE levels. In multivariate models, summation operatorPBDE levels were positively associated with age, years consuming sport fish, shellfish meals, and computer use and negatively associated with recent weight loss. Having summation operatorPBDE levels in the highest quintile was independently associated with older age, male gender, consumption of catfish and shellfish, computer use and spending less time indoors. summation operatorPCB and DDE were strongly associated suggesting common exposure routes. The association between summation operatorPBDE and summation operatorPCB or DDE was much weaker and modeling suggested more diverse PBDE sources with few identified multi-contaminant-shared exposure routes. In our cohort Great Lakes sport fish consumption does not contribute strongly to PBDE exposure.     

Laboratory evaluation of zero-valent iron to treat water impacted by acid mine drainage

This study examines the applicability and limitations of granular zero-valent iron for the treatment of water impacted by mine wastes. Rates of acid-neutralization and of metal (Cu, Cd, Ni, Zn, Hg, Al, and Mn) and metalloid (As) uptake were determined in batch systems using simulated mine drainage (initial pH 2.3-4.5; total dissolved solids 14000-16000 mgl(-1)). Metal removal from solution and acid-neutralization occurred simultaneously and were most rapid during the initial 24 h of reaction. Reaction half-lives ranged from 1.50+/-0.09 h for Al to 8.15+/-0.36 h for Zn. Geochemical model results indicate that metal removal is most effective in solutions that are highly undersaturated with respect to pure-metal hydroxides suggesting that adsorption is the initial and most rapid metal uptake mechanism. Continued adsorption onto or co-precipitation with iron corrosion products are secondary metal uptake processes. Sulfate green rust was identified as the primary iron corrosion product, which is shown to be the result of elevated [SO(4)(2-)]/[HCO(3)(-)] ratios in solution. Reversibility studies indicate that zero-valent iron will retain metals after shifts in redox states are imposed, but that remobilization of metals may occur after the acid-neutralization capacity of the material is exhausted.     

Thermal degradation of fluorotelomer treated articles and related materials

This study reports the first known studies to investigate the thermal degradation of a polyester/cellulose fabric substrate ("article") treated with a fluorotelomer-based acrylic polymer under laboratory conditions conservatively representing typical combustion conditions of time, temperature, and excess air level in a municipal incinerator, with an average temperature of 1000 degrees C or greater over approximately 2s residence time. The results demonstrate that the polyester/cellulose fabric treated with a fluorotelomer-based acrylic polymer is destroyed and no detectable amount of perfluorooctanoic acid (PFOA) is formed under typical municipal incineration conditions. Therefore, textiles and paper treated with such a fluorotelomer-based acrylic polymer disposed of in municipal waste and incinerated are expected to be destroyed and not be a significant source of PFOA in the environment.     

Application of multiple-population viability analysis to evaluate species recovery alternatives

Population viability analysis (PVA) is a powerful conservation tool, but it remains impractical for many species, particularly species with multiple, broadly distributed populations for which collecting suitable data can be challenging. A recently developed method of multiple-population viability analysis (MPVA), however, addresses many limitations of traditional PVA. We built on previous development of MPVA for Lahontan cutthroat trout (LCT) (Oncorhynchus clarkii henshawi), a species listed under the U.S. Endangered Species Act, that is distributed broadly across habitat fragments in the Great Basin (U.S.A.). We simulated potential management scenarios and assessed their effects on population sizes and extinction risks in 211 streams, where LCT exist or may be reintroduced. Conservation populations (those managed for recovery) tended to have lower extinction risks than nonconservation populations (mean = 19.8% vs. 52.7%), but not always. Active management or reprioritization may be warranted in some cases. Eliminating non-native trout had a strong positive effect on overall carrying capacities for LCT populations but often did not translate into lower extinction risks unless simulations also reduced associated stochasticity (to the mean for populations without non-native trout). Sixty fish or 5–10 fish/km was the minimum reintroduction number and density, respectively, that provided near-maximum reintroduction success. This modeling framework provided crucial insights and empirical justification for conservation planning and specific adaptive management actions for this threatened species. More broadly, MPVA is applicable to a wide range of species exhibiting geographic rarity and limited availability of abundance data and greatly extends the potential use of empirical PVA for conservation assessment and planning.     

Methods for measuring denitrification: diverse approaches to a difficult problem.

Denitrification, the reduction of the nitrogen (N) oxides, nitrate (NO3-) and nitrite (NO2-), to the gases nitric oxide (NO), nitrous oxide (N2O), and dinitrogen (N2), is important to primary production, water quality, and the chemistry and physics of the atmosphere at ecosystem, landscape, regional, and global scales. Unfortunately, this process is very difficult to measure, and existing methods are problematic for different reasons in different places at different times. In this paper, we review the major approaches that have been taken to measure denitrification in terrestrial and aquatic environments and discuss the strengths, weaknesses, and future prospects for the different methods. Methodological approaches covered include (1) acetylene-based methods, (2) 15N tracers, (3) direct N2 quantification, (4) N2:Ar ratio quantification, (5) mass balance approaches, (6) stoichiometric approaches, (7) methods based on stable isotopes, (8) in situ gradients with atmospheric environmental tracers, and (9) molecular approaches. Our review makes it clear that the prospects for improved quantification of denitrification vary greatly in different environments and at different scales. While current methodology allows for the production of accurate estimates of denitrification at scales relevant to water and air quality and ecosystem fertility questions in some systems (e.g., aquatic sediments, well-defined aquifers), methodology for other systems, especially upland terrestrial areas, still needs development. Comparison of mass balance and stoichiometric approaches that constrain estimates of denitrification at large scales with point measurements (made using multiple methods), in multiple systems, is likely to propel more improvement in denitrification methods over the next few years.     

Assessment of Benthic Infaunal Condition on the Mainland Shelf of Southern California

Benthic infauna were sampled from 251 Southern California Bight (SCB) mainland shelf sites in the summer of 1994. Sample sites were selected using a stratified random design, with the primary strata being depth zone, geography, and proximity to point and non-point discharges. Benthic infaunal condition was assessed using the Benthic Response Index (BRI), and by comparing dominant taxa and community parameters (e.g., number of taxa) among strata. Ninety-one percent of sediments in the SCB were found to contain healthy benthic communities. Most stations with altered benthos were located near river mouths, in Santa Monica Bay, or on the Palos Verdes Shelf. Deviations at sites with altered benthic communities were mostly limited to minor changes in species composition, rather than to large declines in diversity or abundance.     

An Age-Structured Demographic Model for the Endangered Stephens' Kangaroo Rat

Effective conservation of endangered species often is hampered by inadequate knowledge of demography. We extracted information on survival and fecundity from an 18-month, live-trapping study of Dipodomys stephensi , and from this we developed an age-structured demographic model to assess population viability. Adult Stephens' kangaroo rats persisted longer than juveniles, and adult females persisted longer than adult males. Disappearance rates were high in the first months after initial capture. Thereafter, the fraction of animals persisting decreased slowly and in an approximately linear fashion on a semilogarithmic scale, suggesting age-independent mortality factors such as predation. Juvenile persistence did not differ substantially between two years of strikingly different rainfall. Onset of breeding followed the start of winter rains. Length of the breeding season, average number of litters per female, and the fraction of first-year females breeding were much greater in the year of higher rainfall. We propose a birth-pulse demographic model for D. stephensi that distinguishes juvenile and adult age classes. Temporal environmental variation can be modeled adequately with a constant survivorship schedule and variable fecundity determined by yearly precipitation. Several issues should be resolved, however, before conservation decisions are based on the model. Better estimates of juvenile survivorship are critical, the quantitative relationship between precipitation and fecundity must be determined, and the potential for density dependence and source-sink population dynamics must be evaluated.     

Effect of water temperature on the courtship behavior of the Alpine newt Triturus alpestris

Temperature is expected to have an effect on the behavioral patterns of all organisms, especially ectotherms. However, although several studies focused on the effect of temperature on acoustic displays in both insects and anurans, almost nothing is known about how environmental temperature may affect ectotherm visual courtship displays and sexual performance. The purpose of this study was to determine the effect of environmental temperature on the sexual behavior of Alpine newts (Triturus alpestris). We subjected T. alpestris to two different temperatures in controlled laboratory conditions. Temperature had a major effect on both male and female behaviors: at low temperature, the frequencies of several displays, including tail-raising during sperm deposition, are lowered. This variation is caused indirectly by temperature because it is due to female responsiveness, which is temperature-dependent. However, the fanning movement of the males tail during its main courtship display is independent of female behavior: at lower temperatures, the tail beats at a lower rate, but for a longer time. The similar reproductive success (i.e. sperm transfer) at the two temperature ranges indicates that breeding in cold water is not costly but instead allows males and females to mate early in the season. This is particularly adaptive because, in many habitats, the reproductive period is shortened by drying or freezing conditions, which may impair survival of branchiate offspring. This study also demonstrates the necessity of considering environmental parameters when modeling optimality and characteristics of ectotherm behaviors.Communicated by W. Cooper