Specific accumulation of polychlorinated biphenyls and organochlorine pesticides in Japanese common squid as a bioindicator

Organochlorines (OCs) representing Persistent Organic Pollutants (POPs) such as PCBs (polychlorinated biphenyls), DDTs (DDT and its metabolites), CHLs (chlordane compounds), HCHs (hexachlorocyclohexane isomers) and HCB (hexachlorobenzene) were determined in the liver of Japanese common squid (Todarodes pacificus) collected from the waters around Japan (Japan Sea and western North Pacific Ocean). Among OCs concentrations, PCBs (upto 5600 ng/g lipid wt.) were the highest, and those of other OCs were in the order of DDT> CHLs > HCHs > HCB. Studies on growth trend and seasonal variation of OCs in this species suggest a rapid reflection of the pollution levels in seawater where and when they were collected, regardless of body-length and time of collection. These results indicate that Japanese common squid is a suitable bioindicator for monitoring OCs pollution in waters around Japan. With regard to the geographical distribution of OCs in this species collected from waters around Japan, OCs concentrations in specimens from Japan Sea were higher than those from the Pacific Ocean. This result might reflect some existing of local pollution sources of OCs around Japan Sea, and slower water exchange between Japan Sea and open ocean.     

US Army Chemical Corps Vietnam veterans health study: preliminary results

The long-term health consequences of exposure to phenoxyherbicides used in Vietnam has been a great concern to the veterans. In addition to the Air Force Ranch Hand personnel, Army Chemical Corps personnel who served in Vietnam are thought to have had some of the highest herbicide exposures. The Department of Veterans Affairs commenced a study of veterans who served in Vietnam as members of the Army Chemical Corps and a comparison cohort of Army Chemical Corps personnel who served elsewhere. A total of 2872 Vietnam veterans and 2737 non-Vietnam veterans who served in the Army Chemical Corps were identified for inclusion in a telephone health interview survey with a random 20% sample of veterans receiving serum dioxin and other congeners assessments. In a feasibility study which included 284 Vietnam veterans and 281 non-Vietnam veterans, 100 serum assessments were conducted of which 95 were included in the analysis. Vietnam veterans with a history of spraying herbicides were found to have a statistically significant elevation in their current serum 2,3,7,8-TCDD concentrations compared to non-Vietnam veterans without a spray history (P = 0.05). Other 2,3,7,8-substituted dioxins levels were comparable to the levels found in the non-Vietnam veterans. This feasibility study demonstrated that serum dioxin concentrations from a sample of the study participants can be used to identify exposure variables in the health survey that can serve as a surrogate measure of phenoxyherbicide exposure.     

Atmospheric deposition of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls in the Kanto Region, Japan

The atmospheric bulk (dry and wet) deposition of dioxins was investigated at four locations (Tokyo, Yokohama, Tsukuba, and Tanzawa) in the Kanto region (in Japan) over one year using a stainless-steel pot. Annual average polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/PCDF) deposition fluxes were estimated to be from 450 to 1300 ng/m2/yr, and the annual average TEQ fluxes from 5.7 to 17 ng-TEQ/m2/yr at the four locations. The PCDD/PCDF deposition flux was higher in winter than in summer. The deposition flux could be related to ambient temperature, particularly for less chlorinated PCDDs/PCDFs, while the deposition flux is not necessarily related to the amount of precipitation. The PCDD/PCDF deposition flux increased as the particle deposition flux increased, for the winter samples. Based on the ratio of the PCDD/PCDF deposition fluxes to the particle deposition fluxes, the contribution of the reentrainment of soil particles to the TEQ of PCDD/PCDF deposition was considered to be negligible in this region. Based on the air concentrations monitored near our deposition sampling points by the municipalities, the ratio of the annual deposition flux to the annual average air concentration was roughly estimated to be 0.082 cm/s. The range of deposition flux in the Kanto region was estimated to be from 1.5 to 31 (median: 9.8) ng-TEQ/m2/yr based on the range of air concentration data measured by the municipalities. The total annual deposition flux in the entire Kanto region was estimated to range from 50 to 900 g-TEQ/yr (median 320 g-TEQ/yr). This estimated flux was of the same order as the sum of estimated emissions from municipal solid waste incinerators and industrial waste incinerators in the Kanto region. The contributions of dioxin-like PCBs in Yokohama, Tsukuba, and Tanzawa depositions were less than 10% of the total TEQ; however, in Tokyo it was almost equal to or more than 50%.     

Non-aqueous-phase-liquid breakthrough during evaporative drying of clay barriers

In this study, an attempt has been made to model a real field scenario, whereby an initially almost saturated clay liner in a waste site is gradually drying, due to evaporation at its lower boundary. A detailed conceptual model that deals with the penetration and breakthrough of non-aqueous-phase-liquid (NAPL) in clay liners is introduced. Water content of clay samples was monitored during ambient evaporation through apertures at the base of sample holders. Clay drying rate served as the primary parameter for the NAPL breakthrough study. The interconnection between drying rates, structural damage formation (cracks and suction) and NAPL penetration is especially addressed. The processes taking place in the clay samples during drying appear to be associated with the capillary effects between the different fluid phases in the vicinity of either the NAPL-clay or the clay-air boundaries. A conceptual model of NAPL penetration and breakthrough of the clay layer has been considered, based on both indirect and direct observations of structural damages produced on either clay boundaries. A mutual interaction between these two boundaries is suggested and discussed. NAPL breakthrough is suggested to take place through cracks initiated on the upper soil surface.     

MIRABEL: models for integrated review and assessment of biodiversity in European landscapes

In this paper, we present the methodology and some results from the application of an integrating conceptual framework, MIRABEL, to analyze the consequences of environmental change for biodiversity. For 28 European countries, MIRABEL tabulates changes in the status of threatened habitats predicted to result from 10 environmental pressures. Regional variations in the severity of the pressures and impacts are taken into account by compiling separate impact tables for each of 13 Ecological Regions. Results suggest that agricultural intensification is one of the main threats, however, differences recorded by MIRABEL in the intensity of the pressures, their rate of change and their past and expected impacts on biodiversity in the various Ecological Regions is telling evidence of Europe's biogeographical variety, and of the need to take this into consideration when assessing environmental change.     

Possibilities for improving nitrogen use from organic materials in agricultural cropping systems

Nitrogen release from organic nutrient sources in soil is influenced by a range of factors such as soil temperature and moisture, and chemical composition of the organic material. Chemical composition can, to a certain degree, be controlled to increase the synchronization of nitrogen (N) release with plant N demand, whereas climatic factors cannot be controlled and so must be taken into account when planning management measures. In this paper, we discuss different ways to affect N release through manipulation of the chemical composition of fresh or pretreated plant materials and animal manures, timing of incorporation, and intentional distribution during application. We conclude by giving an overview of off-farm options that may need to be implemented to achieve improved use of N, especially in agricultural systems with surplus N.     

The recovery of ammonia and hydrogen sulfide from ground-level area sources using dynamic isolation flux chambers: bench-scale studies

Controlled bench-scale laboratory experiments were conducted to evaluate the recovery of ammonia (NH3) and hydrogen sulfide (H2S) from dynamic isolation flux chambers. H2S (80-4000 ppb) and NH3 (5000-40,000 ppb) samples were diffused through the flux chamber to simulate ground level area source emissions while measuring the inlet and outlet flux chamber concentrations simultaneously. Results showed that the recovery of H2S during a 30-min sampling time was almost complete for concentrations >2000 ppb. At the lowest concentration of 80 ppb, 92.55% of the H2S could be recovered during the given sampling period. NH3 emissions exhibited similar behavior between concentrations of 5000-40,000 ppb. Within the 30-min sampling period, 92.62% of the 5000-ppb NH3 sample could be recovered. Complete recovery was achieved for concentrations >40,000 ppb. Predictive equations were developed for gas adsorption. From these equations, the maximum difference between chamber inlet and outlet concentrations of NH3 or H2S was predicted to be 7.5% at the lowest concentration used for either gas. In the calculation of emission factors for NH3 and H2S, no adsorption correction factor is recommended for concentrations >37,500 ppb and 2100 ppb for NH3 and H2S, respectively. The reported differences in outlet and inlet concentration above these ranges are outside the fullscale sensitivity of the gas sensing equipment. The use of 46-90 m of Teflon tubing with the flux chambers has apparently no effect on gas adsorption, because recovery was completed almost instantaneously at the beginning of the tests.     

Photodegradation of pentachlorophenol and its degradation pathways predicted using density functional theory

The objectives of the present research were (i) to report the mass balance of chlorine during pentachlorophenol (PCP) photodegradation and (ii) to reveal the photodegradation pathway experimentally with a theoretical proof based on the density functional theory (DFT). The chlorine of PCP was completely mineralized to produce chloride ions after 24h of UV irradiation. As intermediates, 2,3,5,6-tetrachlorophenol, 2,3,4,6-tetrachlorophenol and 2,5-dichlorophenol were identified. At least 80% of the chlorine balance during PCP photodegradation was accounted by PCP, these intermediates, and chloride ions. A DFT calculation showed differences in the C-Cl bond dissociation energy level and the positions of respective PCP molecular and the PCP intermediates. The dechlorination intermediates predicted using the calculated C-Cl bond dissociation energy were consistent with those experimentally confirmed, indicating the feasibility of this theoretical method in predicting the dechlorination pathway.     

Equilibrium and kinetic studies on the adsorption of aniline compounds from aqueous phase onto bifunctional polymeric adsorbent with sulfonic groups

In the present study, a hydrophilic bifunctional polymeric resin (LS-2) with sulfonic groups was synthesized, and the adsorption performance of three aniline compounds, aniline, 4-methylaniline, and 4-nitroaniline onto LS-2 was compared with that on the commercial Amberlite XAD-4. The uptake of the aniline compounds on LS-2 is a procedure of coexistence of physisorption and chemisorption and obeys the pseudo-second order rate equation, while the uptake of the compounds on XAD-4 is merely a physical adsorption and follows the pseudo-first order rate equation. All the isothermal data fit well with the Freundlich model, and the values of K(F) of the compounds adsorbing on LS-2 are much higher than those on XAD-4 suggesting the higher adsorbing capacities on LS-2 than those on XAD-4, which may be attributed to the microporous structure and the polar groups on the network of LS-2 resin. Dynamic adsorption and desorption studies for aniline on LS-2 show that the breakthrough adsorption capacity and the total adsorption capacity are 0.96 and 1.24 mmol per milliliter resin, respectively. Nearly 100% regeneration efficiency for the adsorbent was achieved by 5% hydrochloric acid.     

Modelling the environmental degradation of water contaminants. Kinetics and mechanism of the riboflavin-sensitised-photooxidation of phenolic compounds

The aerobic visible-light-photosensitised irradiation of methanolic solutions of either of the phenolic-type contaminants model compounds (ArOH) p-phenylphenol (PP), p-nitrophenol (NP) and phenol (Ph), and for two additional phenolic derivatives, namely p-chlorophenol (ClP) and p-methoxyphenol (MeOP), used in some experiments, was carried out. Employing the natural pigment riboflavin (Rf) as a sensitiser, the degradation of both the ArOH and the very sensitiser was observed. A complex mechanism, common for all the ArOH studied, operates. It involves superoxide radical anion (O₂^√−) and singlet molecular oxygen (O₂(¹Δ_g)) reactions. Maintaining Rf in sensitising concentrations levels (≈0.02 mM), the mechanism is highly dependent on the concentration of the ArOH. Kinetic experiments of oxygen and substrate consumption, static fluorescence, laser flash photolysis and time-resolved phosophorescence detection of O₂(¹Δ_g) demonstrate that at ArOH concentrations in the order of 10 mM, no chemical transformation occurs due to the complete quenching of Rf singlet excited state. When ArOH is present in concentrations in the order of mM or lower, O₂^√− is generated from the corresponding Rf radical anion, which is produced by electron transfer reaction from the ArOH to triplet excited Rf. The determined reaction rate constants for this step show a fairly good correlation with the electron-donor capabilities for Ph, PP, NP, ClP and MeOP. In this context, the main oxidative species is O₂^√−, since O₂(¹Δ_g) is quenched in an exclusive physical fashion by the ArOH. The production of O₂^√− regenerates Rf impeding the total degradation of the sensitiser. This kinetic scheme could partially model the fate of ArOH in aquatic media containing natural photosensitisers, under environmental conditions.