Estimation of environmentally relevant chemical properties of veterinary ionophore antibiotics

Environmental Science and Pollution Research - Monensin (MON) and salinomycin (SAL), known as polyether ionophore antibiotics (IPAs), are extensively used in livestock industry and can enter the...     

Biodegradability and transformation of human pharmaceutical active ingredients in environmentally relevant test systems

Human pharmaceutical active ingredients that are orally or parenterally administered may be metabolised in the body and after excretion may be further transformed in the receiving environmental compartments. The optimal outcome from an environmental point of view—complete mineralisation—is rarely observed. Small molecule pharmaceuticals are commonly not readily biodegradable according to Organisation for Economic Cooperation and Development (OECD) 301 tests. However, primary transformation is often observed. To gain information on the transformation of active ingredients in the environment, long-term studies like transformation in aquatic water/sediment systems according to OECD guideline 308 are required for the environmental risk assessment for human active pharmaceutical ingredients. Studies received until mid 2010 as part of the dossiers for marketing authorisation applications were evaluated concerning transformation products. The evaluation revealed that in 70 % of the studies, at least one transformation product (TP) is formed above 10 % of the originally applied dose, but in only 26 % of the studies are all TP identified. The evaluation also revealed that some TP of pharmaceutical active ingredients show a considerably longer DT₅₀ compared to the parent compound. An example is the TP (val)sartan acid that is formed from an antihypertensive compound.     

Effects of multigenerational exposures of D. magna to environmentally relevant concentrations of pentachlorophenol

The re-emergence of schistosomiasis has given rise to ubiquitous concentrations of the primary control agent pentachlorophenol (PCP) in the environment, especially in the surface waters of China. In this study, the effects of environmentally relevant concentrations of PCP, namely, 0.0002, 0.002, 0.02, 0.2, and 2 μmol/L on survival, age at first reproduction, fecundity, length of mothers, and number of molts of Daphnia magna were studied over three generations. The survival of D. magna exposed to 2 μmol/L was significantly affected in the three generations. Toxic effects were enhanced in later generations. Age at first reproduction of F ₁ and F ₂ D. magna was significantly slower than that of the controls. The total number of offspring per female exposed to concentrations of 0.002 μmol/L or greater was less (23.5 to 67.6, 9.4 to 73.7, and 3.6 to 83.7 %) than that of the controls in the F ₀, F ₁, and F ₂ generations, respectively. The body length of mothers significantly decreased (4.7 to 6.8, 9.6 to 15.1, and 13.3 to 23.2 %) after exposure to 0.002 μmol/L or greater than those of unexposed individuals in the F ₀, F ₁, and F ₂ generations, respectively. Dose–response relationships between concentrations of PCP and length and number of molts of D. magna were observed in the F ₀ to F ₂ generations. PCP concentrations on the surface waters of China caused adverse effects to D. magna, which increased over successive generations. Significant effects were observed in the third generation. The multigenerational studies were more sensitive than the single-generation experiments. Thus, multigenerational exposure may be more predictive of chronic exposure under field conditions.     

Direct measurement of octanol-water partition coefficients of some environmentally relevant brominated diphenyl ether congeners

Octanol-water partition coefficients (K(OW)) of nine environmentally relevant brominated diphenyl ether (BDE) congeners present in two technical mixtures were directly measured using a slow-stir technique. LogK(OW) values of tri- to heptabrominated BDE congeners ranged from 5.74 to 8.27, and were related to bromine content by the equation logK(OW)=0.621(#Br)+4.12(R(2)=0.970). The directly determined K(OW) values were generally lower than those calculated using fragment constant methods, particularly at higher levels of bromine substitution. The quasi-experimental approach of using fragment constants to modify a "backbone" compound of known K(OW) was much more successful than using the fragment constants to "build" the entire molecule. The tri- and tetrabrominated congeners are in the range of optimum bioaccumulation potential.     

环境中有机污染物的半导体光催化降解研究进展

应用半导体二氧化钛光催化剂促进氧化降解环境中常见有机污染物是一种有效的清洁处理技术,对光催化活性的半导体的必要性质,影响光催化效率的内在因素以及反应器,反应条件等方面的因素进行了讨论。     

Home transport and wastage: environmentally relevant household activities in the life cycle of food

In environmental systems analysis of food production systems, the consumer phase (home transport, cooking, storing, and wastage) is an important contributor to the total life-cycle environmental impact. However, households are the least investigated part of the food chain. Information gathering about households involves difficulties; the number of households is large, and food-related activities are embedded in other household activities. In cooperation between researchers from environmental systems analysis and consumer research, Swedish households were surveyed by questionnaire, diary, and interviews. Data on home transport of food and wastage were collected. The average weekly driving distance was 28 to 63 km per household, depending on how trips made in conjunction with other errands are allocated. The wastage of prepared food ranged between 0 and 34% for different food categories, and wastage from storing between 0 and 164% (more food was discarded, e.g. by cleaning out a cupboard, than consumed). In both cases dairy products scored highest.     

Evidence of immunomodulation in nestling American kestrels (Falco sparverius) exposed to environmentally relevant PBDEs

We investigated whether exposure to environmentally relevant polybrominated diphenyl ethers (PBDEs) causes immunomodulation in captive nestling American kestrels (Falco sparverius). Eggs within each clutch, divided by laying sequence, were injected with safflower oil or penta-BDE congeners-47, -99, -100, and -153 dissolved in safflower oil (18.7 microg sigmaPBDEs/egg) approximating Great Lakes birds. For 29 days, nestlings consumed the same PBDE mixture (15.6+/-0.3 ng/g body weight per day), reaching sigmaPBDE body burden concentrations that were 120x higher in the treatment birds (86.1+/-29.1 ng/g ww) than controls (0.73+/-0.5 ng/g ww). PBDE-exposed birds had a greater PHA response (T-cell-mediated immunity), which was negatively associated with increasing BDE-47 concentrations, but a reduced antibody-mediated response that was positively associated with increasing BDE-183 concentrations. There were also structural changes in the spleen (fewer germinal centers), bursa (reduced apoptosis) and thymus (increased macrophages), and negative associations between the spleen somatic index and sigmaPBDEs, and the bursa somatic index and BDE-47. Immunomodulation from PBDE exposure may be exacerbated in wild birds experiencing greater environmental stresses.     

Metallothionein expression in Aspergillus exposed to environmentally relevant concentrations of heavy metals at different pH levels

Environmental Science and Pollution Research - Heavy metal pollution represents a health threat. Many fungal species are capable of tolerating various heavy metals, especially if they are isolated...     

Evaluating the impacts of some environmentally relevant factors on the availability of bisphenol A with negligible-depletion SPME

The effect of some environmentally relevant factors including salinity, pH, and humic acids on the availability of bisphenol A (BPA) was evaluated by using the negligible-depletion solid-phase microextraction (nd-SPME) biomimetic method. With the variation of salinity (0–500 mM NaCl) and pH (5.0–8.5) of aqueous solutions, the partition coefficients of BPA between the nd-SPME fiber and the aqueous solution varied in the range of log D = 3.55–3.86, which indicates that the salinity and pH can influence the availability of BPA. By using Acros humic acid as model dissolved organic matter (DOM), it was also demonstrated that the environmental factors such as salinity and pH could affect the partitioning of BPA between DOM and aqueous solutions. The determined partition coefficients of BPA between dissolved organic carbon (DOC) and aqueous solutions were in the range of log D_DOC = 4.03–5.60 for Acros humic acid solutions with 1–50 mg l⁻¹ DOC. The influence of salinity and pH on log D_DOC was more significant at low concentration (0–5 mg l⁻¹) of DOC.     

Biodegradability of the antioxidant diaryl-p-phenylene diamine using a modified inherent biodegradation method at an environmentally relevant concentration

The chemical product diaryl-p-phenylene diamine (DAPD), produced by The Goodyear Tire & Rubber Company as POLYSTAY 100® (CAS 68953-84-4), is employed as an antidegradant in polymers used in tires and industrial rubber products. Previous evaluations pertaining to the ecological fate of DAPD indicated a lack of biodegradative activity in aquatic media. In order to further pursue the biodegradation potential of DAPD, it was deemed necessary to enhance the sensitivity of the aquatic biodegradation assay through (a) employment of a radiotracer of the test substance, and (b) optimisation of conditions for achieving maximal solubilisation of test material in the aquatic media of the incubation vessels. Test vessels were prepared according to the OECD ready biodegradability test guidelines, with DAPD added on silica gel at concentrations of 10 or 100 μg L⁻¹, together with a surfactant to aid solubilisation. After 63 d incubation up to 37% mineralisation was measured and up to 29% of the applied radioactivity was incorporated into cell biomass. Also, after 28 d no DAPD could be measured in solution by radio-TLC and HPLC–MS. These three results demonstrate that the antioxidant DAPD undergoes microbiologically mediated biodegradation and is highly unlikely to persist in the environment.     

The effects of antibiotic cocktails at environmentally relevant concentrations on the community composition and acetate biodegradation kinetics of bacterial biofilms

Antibiotics and antibacterials are present in water bodies worldwide but little is known about their effects on the biological processes often used to treat water. In this research, the effect of antibiotics on bacterial activity and community structure was investigated by growing biofilms in the presence and absence of a mixture of three compounds (sulfamethoxazole, erythromycin, and ciprofloxacin) in a continuous-flow rotating annular bioreactor fed acetate as a carbon and energy source. Steady-state, surface area-normalized substrate utilization rates for all antibiotic treatments (all at 0.33 μg L^?1, all at 3.33 μg L^?1, and 1 at 3.33 μg L^?1 with the other 2 at 0.33 μg L^?1) were similar to the control experiments. Higher attached biomass levels in the experiments with ciprofloxacin at 3.33 μg L^?1 resulted in lower steady-state biomass-normalized substrate utilization rates in comparison to other runs. Microbial community analyses via automated ribosomal intergenic spacer analysis revealed significant shifts in community structure for the experiments dosed with the highest concentrations of ciprofloxacin, suggesting that the antibiotic selected for more resistant bacterial strains. The results of this research also suggest that mixtures of antibiotics at the sub-μg L^?1 concentrations typically observed in surface waters are unlikely to affect biological process performance, at least in terms of the degradation of easily assimilable compounds. Conversely, changes to community structure and biofilm quantity might be expected with ciprofloxacin at μg L^?1 concentrations.     

Effects of environmentally relevant concentrations of the xeno-androgen, methyldihydrotestosterone, on male and female mating behavior in Xenopus laevis

Endocrine disrupting compounds (EDCs) are well known to interfere with the hormone system of aquatic vertebrates and to affect their reproductive biology. 17α-Methyldihydrotestosterone (MDHT) is a widely used model compound for the assessment of androgenic EDCs, because it binds with high affinity to nuclear androgen receptors. It was previously shown to affect various aspects of reproductive biology in aquatic vertebrates, however, evidence for MDHT affecting mating behavior of aquatic vertebrate species is lacking. In order to test the assumption that MDHT affects reproductive behavior of aquatic vertebrates, we exposed male and female Xenopuslaevis to three environmentally relevant concentrations of MDHT (30.45 ng L⁻¹, 3.05 μg L⁻¹ and 30.45 μg L⁻¹). In males, MDHT at all concentrations led to enhanced levels of advertisement calling and decreased the relative proportions of rasping, a call type characterizing a sexually unaroused state of the male, indicating an increase in sexual arousal of MDHT exposed males. Temporal and spectral parameters of the advertisement call itself, however, were not affected by MDHT exposure. In females, MDHT (30.45 ng L⁻¹) did not have any effects, while MDHT at 3.05 μg L⁻¹ increased female receptivity, increased the duration of time females spent close to the speaker playing male advertisement calls and reduced their latency to respond. MDHT at 30.45 μg L⁻¹, on the other hand, decreased female receptivity and increased their latency to respond. In summary, this study illustrates that exposure to environmentally relevant concentrations of the androgenic EDC MDHT affects male and female mating behavior of X. laevis. Hence, we suggest that nonaromatizable androgens might play a direct and predominant role in the physiology and regulation of reproduction not only in male but also in female frogs.     

Cork stoppers as an effective sorbent for water treatment: the removal of mercury at environmentally relevant concentrations and conditions

The technical feasibility of using stopper-derived cork as an effective biosorbent towards bivalent mercury at environmentally relevant concentrations and conditions was evaluated in this study. Only 25 mg/L of cork powder was able to achieve 94 % of mercury removal for an initial mercury concentration of 500 μg/L. It was found that under the conditions tested, the efficiency of mercury removal expressed as equilibrium removal percentage does not depend on the amount of cork or its particle size, but is very sensitive to initial metal concentration, with higher removal efficiencies at higher initial concentrations. Ion exchange was identified as one of the mechanisms involved in the sorption of Hg onto cork in the absence of ionic competition. Under ionic competition, stopper-derived cork showed to be extremely effective and selective for mercury in binary mixtures, while in complex matrices like seawater, moderate inhibition of the sorption process was observed, attributed to a change in mercury speciation. The loadings achieved are similar to the majority of literature values found for other biosorbents and for other metals, suggesting that cork stoppers can be recycled as an effective biosorbent for water treatment. However, the most interesting result is that equilibrium data show a very rare behaviour, with the isotherm presenting an almost square convex shape to the concentration axis, with an infinite slope for an Hg concentration in solution around 25 μg/L.     

Effects of environmentally relevant concentrations of metallic compounds on the flatfish Scophthalmus maximus: biomarkers of neurotoxicity,oxidative stress and metabolism

Flatfish species, such as the turbot (Scophthalmus maximus), are common targets for toxic effects, since they are exposed through the food chain (ingestion of contaminated preys) and are in direct contact with the waterborne contaminant and sediments. Furthermore, these fish species live in close proximity to interstitial water that frequently dissolves high amounts of contaminants, including metals. Despite this significant set of characteristics, the present knowledge concerning flatfish contamination and toxicity by metals is still scarce. To attain the objective of assessing the effects of metals on a flatfish species, S. maximus specimens were chronically exposed to lead, copper and zinc, at ecologically relevant concentrations, and biochemical (oxidative stress: catalase and glutathione S-transferases activities, and lipid peroxidation; neurotoxicity: cholinesterase activity) parameters were assessed on selected tissues (gills and liver). Copper had no significant effects on all tested parameters; lead was causative of significant increases in liver GSTs activities and also in lipoperoxidation of gill tissue; exposure to zinc caused a significant increase in catalase activity of gill tissue. None of the tested metals elicited noteworthy effects in terms of neurotoxicity. The obtained results showed that only the metal lead is of some environmental importance, since it was able to cause deleterious modifications of oxidative nature at relevant concentrations.     

Effects of environmentally relevant levels of polyethylene microplastic on Mytilus galloprovincialis (Mollusca: Bivalvia): filtration rate and oxidative stress

Environmental Science and Pollution Research - The objective of the present study was to evaluate the potential toxic effects of polyethylene microplastics (PE-MPs) (40–48 μm) on the...     

The n-octanol and n-hexane/water partition coefficient of environmentally relevant chemicals predicted from the mobile order and disorder (MOD) thermodynamics

The quantitative thermodynamic development of the mobile order and disorder theory in H-bonded liquids is extended in order to predict the partition coefficient. With respect to the classical predictive methods, the great advantage of the present approach resides in the possibility of predicting partition coefficient not only in the reference n-octanol/water partitioning system, but also in any mutually saturated two-phase system made up of two largely immiscible solvents. Constructed from the various free energy contributions encoded in the distribution process, the model furthermore provides a useful tool to understand both the origin and the factors, like the solute molar volume, that determine the partitioning of non-electrolytes between two immiscible liquid phases. From the comparison of the relative magnitude of the terms which contribute to the overall log P value, much information can also be gained concerning the variation of the partition coefficients of the same substances in different distribution systems. For example, the model has successfully been applied to the log P prediction of a number of environmentally important chemicals of varying structure, size and chemical nature in the n-octanol/water and n-hexane/water systems. Whatever the complexing or non-complexing substances studied, the hydrophobic effect always represent the driving force that rules distribution processes in the aqueous environments. As the dominant contribution to the partition coefficient in any organic/aqueous binary system, it is evidenced why hydrophobicity is usually considered to be a good measure of lipophilicity.     

Synthesis of fluorinated polybrominated diphenyl ethers (F-PBDEs) as internal standards for environmental analysis

Polybrominated diphenyl ethers (PBDEs) have become widely distributed as environmental contaminants due to their wide-spread use as flame retardants. Their structural similarity to other halogenated organic pollutants, for example polychlorinated biphenyls (PCBs), has led to speculation that they may have similar toxicological properties and effects. Recent focus on PBDEs as possible priority pollutants has also led to an increasing need for reference standards of PBDEs for toxicological studies and for environmental analysis. In this work we synthesized a series of fluorinated PBDEs (F-PBDEs) which can be used as possible internal standards, as an alternative to high-cost alternatives, such as the (13)C-labelled analogues. F-PBDEs have been synthesized by using different coupling reactions and by bromination of fluorinated starting materials.