Clam‐sediment accumulation factors for polychlorinated biphenyl congeners at a contaminated estuarine marsh

Clam‐sediment accumulation factors for hexa‐, hepta‐ and octa‐chlorobiphenyls were estimated at an intertidal marsh that has been contaminated with Aroclor 1268. Accumulation factors for PCB congeners with K _ow > 6.5 were in the range of 0.07–0.88, indicating that their uptake was hindered by steric factors, contamination levels, non‐equilibrium conditions and stronger affinity to sediment organic carbon. Biota‐sediment accumulation factors (BSAFs) were negatively correlated with log K _ow of superhydrophobic PCB congeners. BSAFs estimated based on 2,3,7,8‐TCDD equivalents of PCBs were 2‐fold greater than those derived from total PCB concentrations.     

Improvement of sampling and analytical methods for polychlorinated dibenzo‐p‐dioxins and dibenzofurans in environmental samples and its quantitative evaluation

Sampling of PCDDs/Fs in flue gas from a MSW incinerator was conducted using a modified apparatus of the 5 train method, which has been widely used for the sampling of PCDDs/Fs emission. In the atmosphere a high volume air sampler with special packings was used. Collection efficiencies of PCDDs/Fs were more than 98% for both samplers, using ¹³C₁₂—PCDD reference standard isomers. It was suggested that these sampling methods were adaptable for the measurements of PCDDs/Fs at sources and in the environment. To validate the applicability of existing methodologies on the PCDD/F determination, interlaboratory comparisons were undertaken. From high resolution GC/MS analysis, 2,3,7,8‐TCDD concentrations in reference ash samples were 0.052±0.013 ng/g as comparable results between the laboratories. In addition, the daily intakes of PCDDs/Fs for exposed persons in the MSW incineration facilities in Japan were estimated ranging of 0.053 to 0.28 pg/kg/day by the international toxic equivalent calculations.     

Mass spectrometric isotope dilution analysis for accurate determination of elements in environmental samples†

The application of mass spectrometric isotope dilution analysis in environmental analytical chemistry is described. Different ionization methods used in mass spectrometry for isotope dilution analysis and the advantage of isotope dilution analysis owing to its accuracy are discussed. The principle of the isotope dilution technique is explained using thallium analysis as an example. Possible methods of sample decomposition for organic and inorganic matrices and of element separation are given. Using lead, cadmium and thallium analyses as examples the application of mass spectrometric isotope dilution analysis for determination of toxic metals in environmental samples is shown. The determination of chloride and bromide traces in snow is given as an example of non‐metal analysis. The possibility of determining pure elements by the isotope dilution technique using a long‐lived radioactive isotope as a spike is discussed.     

Effects of two different intercropping systems on arbuscular mycorrhizal fungal colonization and polychlorinated biphenyl (PCB) dissipation北大核心CSCD

Polychlorinated biphenyls (PCBs) are typical organic contaminants in the environment. It is indicated that plants and soil microorganisms have a positive synergistic effect on the remediation of PCB-contaminated soil. To investigate the effect of intercropping on arbuscular mycorrhizal (AM) fungal colonization and PCB remediation, a pot-cultivation experiment with two intercropping treatments, corn (Zea mays L.) / ryegrass (Lolium perenne L.) and corn/alfalfa (Medicago sativa L.), and a corn monoculture was conducted in a greenhouse. All treatments were inoculated with Funneliformis mosseae M47V. Plant biomass, root mycorrhizal colonization rate, concentration of PCBs and their homologs in soil, 16S rDNA gene abundance, and community composition measured by Terminal Restriction Fragment Length Polymorphism (T-RFLP) were determined after harvesting the plants. Intercropping significantly increased the root mycorrhizal colonization rate and plant biomass of corn (P < 0.05), as well as the available N content of the soil. A significant difference of the bacterial community composition was found among different treatments (P < 0.05). Compared with corn monoculture, corn/alfalfa intercropping significantly increased soil bacteria abundance (P < 0.05). The dissipation rates of total PCBs, as well as that of penta-chloro biphenyls were significantly increased in the intercropping treatments, when compared to the corn monoculture treatment. Moreover, corn/ryegrass intercropping has a significantly positive effect on the dissipation of tri-chloro biphenyls. Non-metric multidimensional scaling (NMDS) analysis indicated that the PCBs homologues composition were significantly correlated with the relative abundance of 128 bp and 148 bp T-RFs. Corn intercropping with ryegrass or alfalfa has a positive effect on root mycorrhizal colonization rate and plant biomass of corn. Inoculation of AM fungi in intercropping treatments significantly improved the efficiency of PCB remediation by promoting bacterial abundance and shifting the bacterial community composition. In conclusion, intercropping combined with AM fungi have positive synergistic effects on the remediation of PCB-contaminated soils. © 2018 Science Press. All rights reserved.     

Polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/Fs) in dated environmental samples,and their connection to known sources

This article investigates available environmental data from measurements of the everywhere present contaminants polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/F) in dated trends in sediment, soil and herbage from locales in Europe and North America. The PCDD/F data are examined in relation to potential major PCDD/F sources based on volume: wood and coal, example of natural combustion; pentachlorophenol (PnCP), example of chlorinated aro‐matics; and polyvinyl chloride (PVC) pyrolysis, example of chlorinated aliphatic. Collected PCDD/F data of congener sums and 2, 3, 7, 8‐substituted congener (PCDD/F profiles) have been investigated with multivariate methods: principal component analysis (PCA) and partial least squares projection to latent structures model (PLS). The results show that PCDD/F data from 12 locales can be separated in one to three independent profiles. Normally one profile is related to the PCDD/F found in PnCP and another to combustion. A subtype of the ‘PnCP’ and ‘combustion’ profiles indicates PCDD/F contributions from PVC‐related combustions. The environmental profiles exhibit some differences from the suggested sources. The relatively unprotected PCDD/F related to PnCP is suggested to have passed photolytic and/or thermal dechlorinations. Lower‐chlorinated congeners in environmental profiles related to combustion appear to have been influenced by environmental distribution processes. PCDD/F data before industrial production of chlorinated organics have only limited similarity to PCDD/F in technical PnCP profiles; an average 4.6% of the PCDD/F is related to PnCP. This suggests that PnCP similarity in recent deposition profiles cannot be a result of environmental transformation. The average proportion of PnCP‐related PCDD/F profile in recent depositions is 35% with North America high (average 57%) and Europe low (average 24%).     

Characterisation and classification of hoarfrost samples collected in Poland (2003–2005) by discriminant analysis

Discharges of nutrients, urea, dissolved organic matter and heavy metals by a sewage underwater pipeline are analysed in comparison to environmental conditions in a shallow coastal zone. Variable thermo-haline stratifications of the water column and currents in upper (2.62–34.97 cm s^?1) and deeper (0.83–10.91 cm s^?1) layers drive vertical diffusion and lateral transport of wastewaters. Loads of reactive phosphorus (0.13 tons d^?1) and ammonium (1.62 tons d^?1) by the pipeline are not negligible compared to the major river loads in the gulf. High concentrations of urea (≤11.51 μmol N dm^?3) were found in the area of wastewater release. Ammonium uptake (6.14–534 nmol N dm^?3 h^?1) strongly exceeded nitrate uptake (0.19–138 nmol N dm^?3 h^?1), indicating that discharges of ammonium by the pipeline are actively assimilated by plankton community even at low levels of light. Distribution of Zn (≤27.7 ppb), Cu (≤25.6 ppb), Cd (≤0.80 ppb) and Pb (≤13.5 ppb) in the water column and the measurement of their complex-forming capacity in seawater did not indicate a persistent perturbation of the pelagic environment due to heavy metals.     

PCB and PCT levels in cultivated and free‐living mussels of galicia (North west Spain)

PCB and PCT residues were measured in free‐living (FM) and cultivated mussels (CM) from ten sites in Galicia by gas chromatography with electron capture detector and capillary column. The level of PCB₁₂₆₀ and PCT₅₄₆₀ in FMs increases going from Muros‐Noya to Vigo estuarine bay. There was a trend of increase from north to south.     

Patterns of serum calcium fractions,magnesium, phosphates and albumin in non‐insulin dependent diabetics (Nidd)

Blood level of calcium fractions (ionized and bound), phosphates, magnesium and albumin were measured in non‐insulin dependent diabetic patients (NIDD). Results were compared with healthy controls to elucidate the pathogenesis of probable changes of these elements. Total ionized calcium and magnesium showed significant decrease (p<0.001, p<0.05 and p<0.05) respectively. Phosphates showed non‐significant decrease while albumin reported nearly similar results. Positive correlation between inorganic phosphates and ionized calcium (r = 0.48, p<0.05) was observed only in healthy control group, not in diabetics. This may be attributed to alteration of ions excretions under diabetic condition through unknown mechanism. Additive increase of heparin sodium units in vitro to normal blood resulted in progressive fall in ionized calcium. Significant decrease was only observed upon addition of higher unit (5IU/ml). This must be taken into consideration biochemically for plasma determination of ionized calcium.     

Soxhlet extraction parameters’ influence on the recovery of polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/F) from a sediment,and artifact formation of PCDD

Soxhlet extraction of polychlorinated dibenzo‐p‐dioxins/dibenzofurans (PCDD/F) from sediment was studied using a designed experimental set‐up. Three variables were studied: three solvent combinations n‐hexane/methanol, dichloromethane/acetone and toluene/methanol; two extraction times, 8 and 16 h, and addition of bulk substances (sodium carbonate). The extraction efficiency was almost identical in all extractions, with the exception of extraction where toluene/ methanol was combined with sodium carbonate. In these samples a major effect was observed, due to formation of Hx‐, Hp‐ and OCDD isomers. Composition of formed PCDD was similar to PCDD isomers found in pentachlorophenol products.     

Evaluation of linear alkylbenzenesulfonate (LAS) biodegradability in sediment by solid‐phase extraction and HPLC analysis

The linear alkylbenzenesulfonate (LAS) sorption on environmental sediments has been known long ago. Their high concentrations reflect the massive input of these chemicals from household and industrial uses. However few attempts were made to identify biodegradation metabolites of LAS in sediment. In this report, a method for the determination of these compounds in sediment samples by high‐performance liquid chromatography (HPLC) is described. The first step of our work was performed by solid‐phase extraction with octadecyl‐bonded silica (C18) mini‐columns and provided a suitable recovery of LAS (90 ± 5%) and most metabolites. Furthermore, laboratory investigations led to study the behaviour of LAS in sediment. The environmental samples used for this purpose were collected from a pond (named étang de Bolmon) located in the French Mediterranean coast. Our results were in agreement with an aerobic biodegradation process of LAS that occurred only with high values of sediment redox potential and needed the samples to be vigorously shaken to ensure adequate mixing and suspension of particulate material. In a stagnant sediment or under anaerobic conditions, LAS is not degraded. p‐Sulfophenylacetic acid and p‐sulfocinnamic acid were evidenced as predominant metabolites and were found not to be persistent.     

Photochemistry of halogenated benzene derivatives. part xii.∗ effects of sodium nitrite on the environmental phototransformation of bromoxynil (3,5‐dibromo‐4‐hydroxybenzonitrile) herbicide in water: The photoincorporation of nitrite ions into bromoxynil

Photoreactions of the herbicide bromoxynil (3,5‐dibromo‐4‐hydroxybenzonitrile) (1) were extensively studied in water containing various concentrations of sodium nitrite with radiation of wavelengths around 313 nm. In the absence of NaNO₂, the quantum yields for the photodecomposition of the herbicide I amounted to 0.054±0.005, while such data was in the range of 0.047 ±0.005 to 0.023 ±0.003 in the presence of 0.5 to 25.0 × 10^‐3 m of the inorganic salt. These quantum yield data for the phototransformation of 1 without and with the presence of sodium nitrite followed the Stern‐Volmer equation. The rates of the photolytic destruction of bromoxynil (1) in water were slower in the presence than in the absence of NaNO₂. For example, the irradiation of the 7.8 x 10^‐6M aqueous solution of 1 in the presence of 10 mM sodium nitrite gave rise to the production of three main photoproducts, viz., 3‐bromo‐4‐hydroxy‐5‐nitrobenzonitrile (2), 4‐hydroxy‐3‐nitrobenzonitrile (3), and an “unidentified photoproduct”; 4. In the case of this photoreaction of compound 1, the percentages of maximum concentration of the photoproducts 2, 3, and 4 were achieved after 14, 44.5, and 60‐min photolyses of 1, respectively; the starting material 1 completely disappeared after 60‐min photolysis. The photoproducts 2 and 3 were identified through the interpretation of the GC‐MS data. Both thhe mass and FT‐IR spectra of the product 4 indicated the possible presence of a COOH group in 4.     

Observations on metal trends in soil and vegetation samples collected in the vicinity of a hazardous waste incinerator under construction (1996–1998)

The temporal variation in metal concentrations in soil and vegetation samples collected in an area of Catalonia (Spain), which will be under the potential influence of a new hazardous waste incinerator was determined. In 1996 and again in 1998, As, Be, Cd, Cr, Hg, Mn, Ni, Pb, Sn, Tl and V were measured in 40 soil and 40 herbage samples collected at 250–4000 m from the facility at the same sampling points. Data of both surveys and the percentages of variation are here presented for all metals. Results are shown according to the main wind directions in the area, as well as distances from the new facility. During the period 1996–1998, a general decrease was noted for most metals. Only the levels of Hg were significantly increased during this period. The present results will be useful for future surveys aimed to evaluate the environmental impact of metals derived from emissions of the new plant.     

Geochemical fractionation and spectroscopic fingerprinting for evaluation of the environmental transformation of potentially toxic metal(oid)s in surface–subsurface soils

Environmental Geochemistry and Health - The contamination of soil by toxic metal(oid)s has emerged as a major concern worldwide, particularly in developing countries. A metals behavior in the soil...     

The international toxicity equivalency factor (I‐TEF) method for estimating risks associated with exposures to complex mixtures of dioxins and related compounds∗

The International Toxicity Equivalency Factor (I‐TEF) method of risk assessment is a revised interim procedure for assessing the risks associated with exposures to complex mixtures of chlorinated dibenzo‐p‐dioxins and dibenzofurans (CDDs and CDFs). This updated scheme was developed by a working group of the North Atlantic Treaty Organization's Committee on the Challenges of Modern Society and has been officially adopted by the U.S. Environmental Protection Agency (EPA), Canada, Ontario Ministry of the Environment, the Nordic countries, the Netherlands, and the United Kingdom. Prior to the development of the I‐TEF method, at least ten slightly different schemes had been used throughout the world which complicated communication among scientists and regulatory agencies concerning the toxicological significance of complex mixtures of CDDs and CDFs. The I‐TEF approach facilitates risk communication internationally by reducing large volumes of analytical data into a single number‐International Toxicity Equivalents (I‐TEQ). As a result, the I‐TEF method represents an improvement in an already useful risk assessment/regulatory tool.     

Higher education level teaching of (master’s) programmes in sustainable development: analysis of views on prerequisites and practices based on a worldwide survey

The concept of sustainable development (SD) has highly been debated since it was presented 25 years ago, with ‘hard science’ approaches on one side and more process-oriented approaches on the other side. Academic teaching in SD has emerged in response to this in very different contexts, partly mirroring this academic debate. Some master’s programmes in SD take a strong science approach, while other programmes focus on the process of implementing sustainability projects, sometimes connected with forms of action research and teaching. In this article, we identify diverse views on the concept of SD as well as views on most relevant modes of teaching. We discuss core competencies required for sustainability professionals in their working practices and we organise them in three main clusters: Know, Interact and Be (KIB). The article presents the results of a worldwide survey, which addresses these visions on the concept of SD, the capabilities needed for ‘sustainable development professionals’ and the teaching approach needed. The analysis is based on the responses of 54 lecturers and 287 students active in 34 SD master’s programmes on all continents. The results of this worldwide survey are discussed. We observe in practice some gaps between preferences and practice. Looking at what both lecturers and students see as essential topics to address, some topics get relatively less attention (like the population issue). The identified core competencies (KIB) are supported and all addressed in practice, while the ‘Be’ competencies receive relatively less attention. Suggested consequences for academic teaching include a further matching of programmes with perceived needs and bridging the gap between the experienced teaching approaches in practice with such identified needs.     

An integrated GIS for sedimentological and geomorphological analysis of a lagoon environment. Barra de Cananéia inlet region, (Southeastern Brazil)

The aim of this work is to use GIS integration data to characterize sedimentary processes in a SubTropical lagoon environment. The study area was the Cananéia Inlet estuary in the southeastern section of the Cananéia Lagoon Estuarine System (CLES), state of S?o Paulo, Brazil (25°03′S/47°53′W). The area is formed by the confluence of two estuarine channels forming a bay-shaped water body locally called “Trapandé Bay”. The region is surrounded by one of the most preserved tracts of Atlantic Rain Forest in Southwestern Brazil and presents well-developed mangroves and marshes. In this study a methodology was developed using integrated a GIS database based on bottom sediment parameters, geomorphological data, remote sensing images, Hidrodynamical Modeling data and geophysical parameters. The sediment grain size parameters and the bottom morphology of the lagoon were also used to develop models of net sediment transport pathways. It was possible to observe that the sediment transport vectors based on the grain size model had a good correlation with the transport model based on the bottom topography features and Hydrodynamic model, especially in areas with stronger energetic conditions, with a minor contribution of finer sediments. This relation is somewhat less evident near shallower banks and depositional features. In these regions the organic matter contents in the sediments was a good complementary tool for inferring the hydrodynamic and depositional conditions (i.e. primary productivity, sedimentation rates, sources, oxi-reduction rates).     

Diet of intertidal bivalves in the Ría de Arosa (NW Spain): evidence from stable C and N isotope analysis

We used natural abundance measurements of stable carbon and nitrogen isotopes and a short-term ¹⁵N-enrichment experiment to explore the importance of river-derived and autochthonous sources to the diet of intertidal suspension-feeding bivalves in the Ría de Arosa, an oceanic-dominated system in northwest Spain. Highly seasonal and intense phytoplankton "bloom" events occur in this estuary. However, relatively low phytoplankton standing crop and productivity are present during much of the year, suggesting that food sources other than phytoplankton must support bivalves during these periods. Bivalves (Cerastoderma edule, Tapes decussatus, Mytilus galloprovincialis) were sampled quarterly at four intertidal stations along the length of the estuary with increasing distance from the Ulla River. Muscle tissue was consistently enriched in ¹³C and ¹⁵N relative to stomach contents. The stable C isotope values of bivalves indicated that river-derived inputs were, at most, a minor component of diet. These values suggested the potential importance of benthic microalgae to bivalve diet much of the year and the incorporation of ¹⁵N label applied to the sediment surface into stomach contents and muscle tissue in a field experiment supported this conclusion. Other labeled components of the microbenthos such as bacteria could also have been ingested. ¹³C-depleted values of bivalves in May coincided with elevated offshore chlorophyll a concentrations, suggesting the increased use of a phytoplankton source during the spring. We propose that intertidal suspension-feeding bivalves in this estuary use primarily resuspended microbenthos during periods of low phytoplankton concentration, but that phytoplankton increases in relative dietary importance during bloom events.Communicated by P.W. Sammarco, Chauvin     

Multivariate statistical techniques for the evaluation of spatial and temporal variations in water quality of the Mahanadi river–estuarine system (India) – a case study

Spatial and temporal distributions of water quality using multivariate statistical techniques for the evaluation of nutrients (NO₂-N, NO₃-N, NH₄-N, PO₄-P, SiO₄-Si, total N, total P) in relation to some physico-chemical features (DO, BOD, TSS, TDS, SO₄²⁻, Cl⁻) were studied for 31 different stations of the Mahanadi river–estuarine system in the eastern part of India. The seasonal nutrient variations (except SiO₄-Si) exhibit higher values during monsoon season in unpolluted stations and the reverse trends for polluted stations, which are related to agricultural run-off and regional anthropogenic activities respectively. Silicate shows a well defined pattern of distribution with a higher concentration during the monsoon, which is slightly removed from the estuarine water of Mahanadi during the pre-monsoon season. The results of R-mode factor analyses revealed that anthropogenic contributions are responsible for the increase in nutrients and the decrease in DO and pH levels of the water. The magnitude of BOD with respect to total N and P demonstrates the intensity of organic pollution in the system. The removal of silicate in the saline system is clearly visible through factor analysis and the different mode of association of TSS is reflected seasonally. The relationships among the stations are highlighted by cluster analysis, represented in dendograms to categorize different levels of contamination.     

Cobalt speciation assay for human serum,Part II. Method validation in a study of human volunteers ingesting cobalt(II) chloride dietary supplement for 90 days

A new analytical method for determining cobalt (Co) species in human serum by size exclusion chromatography with inductively coupled plasma mass spectrometry (SEC-ICP-MS) was applied to serum samples collected from 12 human volunteers who participated in a Co(II) chloride supplement study involving ingestion of 1 mg Co/day for up to 90 consecutive days. The study protocol included determination of serum total Co by acid digestion followed by ICP-MS. Co speciation assay measurements were conducted for up to 13 time points per individual spanning from one to two weeks before dosing began to two weeks after dosing ceased. The Co speciation assay showed good recovery >91% relative to total Co measurements. Undiluted serum demonstrated uniform fractions of large molecular Co defined as Co bound to albumin and other proteins >50 kDa at 96% and the residual as small molecular Co defined as free Co(II) and <1 kDa Co-complexes for individual serum Co concentrations up to 146 μg/L. There were no dose-related changes in Co distribution. Analysis of the same serum samples with tenfold dilution in 0.1 M acetic acid led to a lower fraction of large molecular Co at 87%, with the difference between diluted and undiluted measurements being 8.4%. The difference noted between undiluted and diluted large molecular Co may be attributed to Co release from albumin. Data demonstrated that large molecular Co was the predominant Co species in both undiluted and diluted human serum over a broad range of in vivo Co concentrations, reflecting high albumin–Co binding capacity. These data validate the Co speciation assay and may be employed in understanding further the toxicokinetics and dose-response relationships for Co species.