Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.     

A Holistic Approach to Hydrocarbon Source Allocation in the Subtidal Sediments of Prince William Sound,Alaska, Embayments

Prince William Sound (PWS), Alaska has an extensive history of human and industrial activity that has produced a complex organic geochemistry record in subtidal sediments of embayments throughout the sound. In addition to contributions from recent oil spills and a regional background of natural petroleum hydrocarbons originating from active hydrocarbon systems in the northern Gulf of Alaska (GOA), pyrogenic and petrogenic PAH were, and continue to be introduced to subtidal sediments at numerous sites of past and present human activities. These sites include villages, fish hatcheries, fish camps and recreational campsites in addition to abandoned settlements, canneries, sawmills, and mines. A holistic approach is used to fingerprint and quantify hydrocarbon contributions from multiple sources in a sediment sample. It involves acquiring a comprehensive understanding of the history of the area to identify potential sources, collection of representative samples, and accurate quantitative analyses of the source and sediment samples for a suite of diagnostic PAH analytes and chemical biomarker compounds. Unlike the deepwater sediments of the sound and GOA, the TOC tool, described elsewhere, does not work as well in some restricted embayments due to their high contents of recent organic matter (ROM). The current study employs a constrained least-squares algorithm to allocate hydrocarbon sources contributing to subtidal sediments collected from PWS embayments in 1991, 1999 and 2000. Results show that sources contributing to the natural petrogenic background are present in the embayments, pyrogenic hydrocarbons including combustion products of diesel are important where human activity was high, and petroleum produced from the Monterey Formation (CA) is present locally. Oil and asphalt shipped from California were widely used for fuel and construction prior to development of the Cook Inlet and North Slope fields. In certain locations that were oiled in 1989, low levels of highly degraded Alaska North Slope crude oil residues attributable to the Exxon Valdez spill remain.     

Phthalate exposure in pregnant women and their children in central Taiwan

Phthalate exposure was found to be associated with endocrine disruption, respiratory effects, reproductive and developmental toxicity. The intensive use of plastics may be increasing the exposure to phthalates in Taiwanese population, particularly for young children.We studied phthalate metabolites in pregnant women and their newborns in a prospective cohort from a medical center in Central Taiwan. One hundred maternal urine samples and 30 paired cord blood and milk samples were randomly selected from all of participants (430 pregnant women). Eleven phthalate metabolites (MEHP, 5OH-MEHP, 2cx-MEHP, 5cx-MEPP, 5oxo-MEHP, MiBP, MnBP, MBzP, OH-MiNP, oxo-MiNP, and cx-MiNP) representing the exposure to five commonly used phthalates (DEHP, di-isobutyl phthalate (DiBP), DnBP, BBP, DiNP) were measured in urine of pregnant women, cord serum and breast milk after delivery, and in urine of their children. Exposure was estimated with excretion factors and correlation among metabolites of the same parent compound. Thirty and 59 urinary samples from 2 and 5 years-old children were randomly selected from 185 children successfully followed.Total urinary phthalate metabolite concentration (geometric mean, μg L⁻¹) was found to be higher in 2-years-olds (398.6) and 5-years-olds (333.7) than pregnant women (205.2). Metabolites in urine are mainly from DEHP. The proportion of DiNP metabolites was higher in children urine (4.39 and 8.31%, ages 2 and 5) than in adults (0.83%) (p < 0.01). Compared to urinary levels, phthalate metabolite levels are low in cord blood (37.45) and milk (14.90). DEHP metabolite levels in women’s urine and their corresponding cord blood are significantly correlated. Compared to other populations in the world, DEHP derived metabolites in maternal urine were higher, while phthalate metabolite levels in milk and cord blood were similar. The level of phthalate metabolites in milk and cord blood were comparable to those found in other populations. Further studies of health effects related to DEHP and DiNP exposure are necessary for the children.     

Comparing the sensitivity of soil invertebrates to pesticides with that of Eisenia fetida

The sole routine testing of the standard earthworm Eisenia fetida for the terrestrial risk assessment of pesticides has been under much debate since other soil invertebrates may be more sensitive than this standard test species. However, the very low availability of laboratory toxicity data for taxa other than E. fetida has greatly hampered sensitivity comparisons. In the present study, the relative tolerance (T_rel) approach was used to enable comparing toxicity thresholds obtained from the US-EPA ECOTOX database, for main terrestrial taxonomic groups and pesticidal types of action (insecticides, fungicides, herbicides, and other) separately. Analyses confirmed previously reported lower and higher sensitivity of collembolans to fungicides and insecticides, respectively. However, various other discrepancies in susceptibility relative to E. fetida were encountered as indicated by species sensitivity distributions and/or calculated 95% confidence intervals of T_rel values. Arachnids and isopods were found to be more sensitive to insecticides, and nematodes to fungicides, as compared to E. fetida. Implications of study findings for the terrestrial risk assessment of pesticides are discussed.     

The role of intergenerational influence in waste education programmes: the THAW project

Whilst the education of young people is often seen as a part of the solution to current environmental problems seeking urgent attention, it is often forgotten that their parents and other household members can also be educated/influenced via home-based educational activities. This paper explores the theory of intergenerational influence in relation to school based waste education. Waste Watch, a UK-based environmental charity (www.wastewatch.org.uk), has pioneered a model that uses practical activities and whole school involvement to promote school based action on waste. This methodology has been adopted nationally. This paper outlines and evaluates how effective school based waste education is in promoting action at a household level. The paper outlines Waste Watch's 'Taking Home Action on Waste (THAW)' project carried out for two and half years in Rotherham, a town in South Yorkshire, England. The project worked with 6705 primary age children in 39 schools (44% of primary schools in the project area) to enable them to take the "reduce, reuse and recycle message" home to their families and to engage these (i.e. families) in sustainable waste management practices. As well as substantial increases in students' knowledge and understanding of waste reduction, measurement of the impact of the project in areas around 12 carefully chosen sample schools showed evidence of increased participation in recycling and recycling tonnages as well as declining levels of residual waste. Following delivery of the project in these areas, an average increase of 8.6% was recorded in recycling set out rates which led to a 4.3% increase in paper recycling tonnages and an 8.7% increase in tonnages of cans, glass and textiles collected for recycling. Correspondingly, there was a 4.5% fall in tonnages of residual waste. Waste Watch's THAW project was the first serious attempt to measure the intergenerational influence of an education programme on behaviour at home (i.e. other than schools' own waste). It clearly shows that household recycling behaviour can be positively impacted by intergenerational influence via a practical school-based waste education model. However, although the model could potentially have a big impact if rolled out nationally, it will require seed funding and the long-term durability of the model has not yet been fully quantified.     

An evaluation of legislative measures on electrical and electronic waste in the People's Republic of China

With the increasing number of recycling mishaps in connection with waste electronic and electrical equipment (WEEE) in the People's Republic of China, it is imperative that the handling and recycling of WEEE be sufficiently regulated in China. Regulations covering three major issues, namely, take-back issues, controls on hazardous substances in WEEE and the assurance of good environmental management in WEEE plants, were promulgated between 2006 and 2008. The evaluation in this country report shows that few of these regulatory measures have performed satisfactorily in terms of enforcement, of public acceptance and of environmental concerns. In brief, the take-back requirements and the associated financial responsibilities are only vaguely defined; the control on hazardous substances and the so-called "environmental expiry date" requirements cannot be properly enforced, and the resources needed to ensure the satisfactory enforcement of the environmental abatement and pollution control requirements in WEEE plants are overwhelming. In addition, the use of a "multiple enforcement body" approach to the control of hazardous substances in WEEE is an indication that the Chinese government lacks the determination to properly enforce the relevant legal requirements.     

Impact of increased collection rates and the use of commingled collection systems on the quality of recovered paper. Part 1: increased collection rates

The recovery and utilization of recovered paper have increased over past decades all over the world due to economic, environmental, and social issues. However, it is well known that an extended recovered paper collection is detrimental to its quality, either by the exploitation of lower quality sources such as households, or the spreading of commingled systems instead of selective collection systems. The influence of these two factors was assessed by analyzing the quality of different recovered paper grades used as raw material in a mill located in Madrid (Spain) producing newsprint and light weight coated paper from recovered paper. Part 1 of the paper deals with the impact of increased collection rates on the quality of recovered paper and Part 2 with the use of commingled collection systems. Results of Part 1 show that increased collection rates have a large impact on the quality of the recovered paper. The quality, measured as total unusable material and moisture contents, had deteriorated very rapidly in only 4 years (2005–2008) as a consequence of increased collection rates. Collection rates increased in Spain from 58.5% to 68.6% during this period, resulting in more than 50% increase of total unusable material and 25% of moisture content. The downgrading of the quality of recovered paper is one of the major threats for extending the current limits of paper recycling. Therefore, future challenge is to increase its availability but maintaining its quality.     

Engineered nanomaterials in rivers--exposure scenarios for Switzerland at high spatial and temporal resolution

Probabilistic material flow analysis and graph theory were combined to calculate predicted environmental concentrations (PECs) of engineered nanomaterials (ENMs) in Swiss rivers: 543 river sections were used to assess the geographical variability of nano-TiO₂, nano-ZnO and nano-Ag, and flow measurements over a 20-year period at 21 locations served to evaluate temporal variation. A conservative scenario assuming no ENM removal and an optimistic scenario covering complete ENM transformation/deposition were considered. ENM concentrations varied by a factor 5 due to uncertain ENM emissions (15%-85% quantiles of ENM emissions) and up to a factor of 10 due to temporal river flow variations (15%-85% quantiles of flow). The results indicate highly variable local PECs and a location- and time-dependent risk evaluation. Nano-TiO₂ median PECs ranged from 11 to 1′623 ng L⁻¹ (conservative scenario) and from 2 to 1′618 ng L⁻¹ (optimistic scenario). The equivalent values for nano-ZnO and nano-Ag were by factors of 14 and 240 smaller.     

Regulation (EC) No. 1107/2009 and upcoming challenges for exposure assessment of plant protection products--Harmonisation or national modelling approaches?

In the new European Pesticide Regulation (EC) No. 1107/2009, the harmonisation of approaches for estimation of the environmental exposure of pesticides is considered a major goal. Several member states currently require their own models for the calculation of predicted environmental concentrations (PEC) in surface water. The variety of methods makes risk evaluations rather time-consuming for both notifiers and evaluating authorities. In the present study we compare surface water concentrations of 19 compounds using EU and country-specific models and risk assessment approaches to evaluate to which extent the resulting estimated exposure concentrations differ. Our results show that EU and country specific approaches and the resulting surface water concentrations differ considerably regarding basic model assumptions and assessment methods. The results indicate that the aimed harmonisation of risk assessment approaches within the EU will be difficult based on current models. New scenarios may help to achieve a harmonisation taking country-specific features into account.     

Photophysical and photochemical properties of the pharmaceutical compound salbutamol in aqueous solutions

Salbutamol is a potent β₂-adrenergic receptor agonist widely used in the treatment of bronchial asthma and chronic obstructive pulmonary disease. An increasing number of studies have detected salbutamol in natural water systems worldwide. Studies have shown that sunlight degrades salbutamol resulting in the formation of products; some showing higher toxicity to bacteria Vibrio fischeri than the parent compound. In this contribution, steady-state absorption and emission techniques, high-performance liquid chromatography, and transient absorption spectroscopy are used to investigate the photochemistry of salbutamol in aqueous buffer solutions at controlled pH values. Ground- and excited-state calculations that include solvent effects are performed to guide the interpretation of the experimental results. Salbutamol is sensitive to UVB light absorption in the pH range from 3 to 12, forming products that absorb light at longer wavelengths than the parent compound. Quantum yields of degradation reveal that the deprotonated species is 10-fold more photo-active than the protonated species. In line with this result, the fluorescence quantum yield of the protonated species is more than an order of magnitude higher than that of the deprotonated species. Transient absorption spectroscopy shows that population of the triplet state occurs with a rate constant of 7.1 × 10⁸ s⁻¹ in the protonated species, while a rate constant of 1.7 × 10¹⁰ s⁻¹ is measured for the deprotonated species. While degradation of the deprotonated species is not affected by the presence of molecular oxygen, a twofold increase in the photodegradation yield of the protonated species in air-saturated conditions is observed.