A Biomimetic Approach to the Detection and Identification of Estrogen Receptor Agonists in Surface Waters Using Semipermeable Membrane Devices (SPMDs) and Bioassay-Directed Chemical Analysis (12 pp)

Goal, Scope and Background Some anthropogenic pollutants posses the capacity to disrupt endogenous control of developmental and reproductive processes in aquatic biota by activating estrogen receptors. Many anthropogenic estrogen receptor agonists (ERAs) are hydrophobic and will therefore readily partition into the abiotic organic carbon phases present in natural waters. This partitioning process effectively reduces the proportion of ERAs readily available for bioconcentration by aquatic biota. Results from some studies have suggested that for many aquatic species, bioconcentration of the freely-dissolved fraction may be the principal route of uptake for hydrophobic pollutants with logarithm n-octanol/water partition coefficient (log Kow) values less than approximately 6.0, which includes the majority of known anthropogenic ERAs. The detection and identification of freely-dissolved readily bioconcentratable ERAs is therefore an important aspect of exposure and risk assessment. However, most studies use conventional techniques to sample total ERA concentrations and in doing so frequently fail to account for bioconcentration of the freely-dissolved fraction. The aim of the current study was to couple the biomimetic sampling properties of semipermeable membrane devices (SPMDs) to a bioassay-directed chemical analysis (BDCA) scheme for the detection and identification of readily bioconcentratable ERAs in surface waters. Methods SPMDs were constructed and deployed at a number of sites in Germany and the UK. Following the dialytic recovery of target compounds and size exclusion chromatographic clean-up, SPMD samples were fractionated using a reverse-phase HPLC method calibrated to provide an estimation of target analyte log Kow. A portion of each HPLC fraction was then subjected to the yeast estrogen screen (YES) to determine estrogenic potential. Results were plotted in the form of 'estrograms' which displayed profiles of estrogenic potential as a function of HPLC retention time (i.e. hydrophobicity) for each of the samples. Where significant activity was elicited in the YES, the remaining portion of the respective active fraction was subjected to GC-MS analysis in an attempt to identify the ERAs present. Results and Discussion Estrograms from each of the field samples showed that readily bioconcentratable ERAs were present at each of the sampling sites. Estimated log Kow values for the various active fractions ranged from 1.92 to 8.63. For some samples, estrogenic potential was associated with a relatively narrow range of log Kow values whilst in others estrogenic potential was more widely distributed across the respective estrograms. ERAs identified in active fractions included some benzophenones, various nonylphenol isomers, benzyl butyl phthalate, dehydroabietic acid, sitosterol, 3-(4-methylbenzylidine)camphor (4-MBC) and 6-acetyl-1,1,2,4,4,7-hexamethyltetralin (AHTN). Other tentatively identified compounds which may have contributed to the observed YES activity included various polycyclic aromatic hydrocarbons (PAHs) and their alkylated derivatives, methylated benzylphenols, various alkylphenols and dialkylphenols. However, potential ERAs present in some active fractions remain unidentified. Conclusions and Outlook Our results show that SPMD-YES-based BDCA can be used to detect and identify readily bioconcentratable ERAs in surface waters. As such, this biomimetic approach can be employed as an alternative to conventional methodologies to provide investigators with a more environmentally relevant insight into the distribution and identity of ERAs in surface waters. The use of alternative bioassays also has the potential to expand SPMD-based BDCA to include a wide range of toxicological endpoints. Improvements to the analytical methodology used to identify ERAs or other target compounds in active fractions in the current study could greatly enhance the applicability of the methodology to risk assessment and monitoring programmes.     

The Society for Environmental Geochemistry and Health Tenth European Meeting University of Edinburgh April 12–15, 1992

The Society for Environmental Geochemistry and Health Tenth European MeetingUniversity of Edinburgh April 12–15, 1992     

Synthesis of maximum water recovery network for batch process systems

Development of maximum water recovery (MWR) networks for continuous processes based on Pinch Analysis has been rather well established. In contrast, less work has been done on the water minimisation problem for batch process systems. This work presents a two-stage procedure for the synthesis of an MWR network for a batch process system, covering both mass transfer-based and non-mass transfer-based water-using processes. The first stage of the synthesis task is to locate the various network targets, which include the overall and interval-based minimum utility targets (fresh water and wastewater flows) as well as storage capacity target using the newly developed time-dependent water cascade analysis (WCA) technique. In the second stage, a new tool called the time-water network is introduced to help in the development of the MWR network to achieve the established utility targets. This new network representation has an advantage of clearly depicting the time-dependent nature of a batch water network.     

Mutual information in the Tangled Nature model

We consider the concept of mutual information in ecological networks, and use this idea to analyse the Tangled Nature model of co-evolution. We show that this measure of correlation has two distinct behaviours depending on how we define the network in question: if we consider only the network of viable species this measure increases, whereas for the whole system it decreases. It is suggested that these are complimentary behaviours that show how ecosystems can become both more stable and better adapted.     

Multivariate analysis for source identification of pollution in sediment of Linggi River,Malaysia

Rapid socioeconomic development in the Linggi River Basin has contributed to the significant increase of pollution discharge into the Linggi River and its adjacent coastal areas. The toxic element contents and distributions in the sediment samples collected along the Linggi River were determined using neutron activation analysis (NAA) and inductively coupled plasma-mass spectrometry (ICP-MS) techniques. The measured mean concentration of As, Cd, Pb, Sb, U, Th and Zn is relatively higher compared to the continental crust value of the respective element. Most of the elements (As, Cr, Fe, Pb, Sb and Zn) exceeded the freshwater sediment quality guideline-threshold effect concentration (FSQG-TEC) value. Downstream stations of the Linggi River showed that As concentrations in sediment exceeded the freshwater sediment quality guideline-probable effect concentration (FSQG-PEC) value. This indicates that the concentration of As will give an adverse effect to the growth of sediment-dwelling organisms. Generally, the Linggi River sediment can be categorised as unpolluted to strongly polluted and unpolluted to strongly to extremely polluted. The correlation matrix of metal-metal relationship, principle component analysis (PCA) and cluster analysis (CA) indicates that the pollution sources of Cu, Ni, Zn, Cd and Pb in sediments of the Linggi River originated from the industry of electronics and electroplating. Elements of As, Cr, Sb and Fe mainly originated from motor-vehicle workshops and metal work, whilst U and Th originated from natural processes such as terrestrial runoff and land erosion.     

Policy and Practice Certainty for Effective Uptake of Diffuse Pollution Practices in A Light-Touch Regulated Country

Environmental Management - Although the link between agriculture and diffuse water pollution has been understood for decades, there is still a need to implement effective measures to address this...     

What motivates farmers to participate in the Nova Scotia environmental farm plan program? Evidence and environmental policy implications

Program stakeholders are interested in better understanding farmers' experience, and factors that affect farmer participation in the relatively new Environmental Farm Plan (EFP) program, implemented in several provinces in Canada. To increase relevance of the research findings to EFP program administrators and policy makers, the research methods emphasised determining whether relationships exist among program-related variables, and how such relationships affect farmers' decision choices and behaviour. Traditional farmer and farm attributes that have contrasting effects in agricultural innovation adoption and conservation management (namely age, and formal education completed), were not associated with EFP program participation. Farm income, years of farming experience, and type of agribusiness managed were associated with participation in the Nova Scotia EFP program. Although program participants tended to have higher incomes, overall, non-financial considerations dominated monetary considerations in Nova Scotia farmers' reasons for participating in the Nova Scotia EFP. Helping to publicize positive farm stewardship practices was reported as the most important reason for participating in the EFP scheme, followed by its use to help improve relationships with non-farming neighbours, and to comply with government environmental regulations. In contrast, and somewhat a surprising finding, minimizing potential farm environmental risk, program administrators' raison d'être for promoting the NS EFP, was ranked the lowest, with no respondent rating that as a "very important" or "extremely important" reason for participating in the EFP program.     

Fate of CL-20 in sandy soils: degradation products as potential markers of natural attenuation

Hexanitrohexaazaisowurtzitane (CL-20) is an emerging explosive that may replace the currently used explosives such as RDX and HMX, but little is known about its fate in soil. The present study was conducted to determine degradation products of CL-20 in two sandy soils under abiotic and biotic anaerobic conditions. Biotic degradation was prevalent in the slightly acidic VT soil, which contained a greater organic C content, while the slightly alkaline SAC soil favored hydrolysis. CL-20 degradation was accompanied by the formation of formate, glyoxal, nitrite, ammonium, and nitrous oxide. Biotic degradation of CL-20 occurred through the formation of its denitrohydrogenated derivative (m/z 393 Da) while hydrolysis occurred through the formation of a ring cleavage product (m/z 156 Da) that was tentatively identified as CH₂N-C(N-NO₂)-CHN-CHO or its isomer N(NO₂)CH-CHN-CO-CHNH. Due to their chemical specificity, these two intermediates may be considered as markers of in situ attenuation of CL-20 in soil.     

A superstructure model for the synthesis of single-contaminant water networks with partitioning regenerators

This paper presents a novel superstructure-based optimization model for the synthesis of industrial water networks with partitioning regenerators. Such regenerators function by splitting a contaminated water stream into a regenerated lean stream and a low-quality reject stream. Membrane separation-based processes are examples of these types of regenerators. The optimization model presented in this work integrates a single, centralized partitioning regenerator with a source–demand superstructure under the assumption that the processes within the plant are of the fixed flow rate type. The formulation is non-linear as a result of the presence of bilinear terms in the regenerator balance equations, but global optimal solutions can be found using commercial software. The features of the model are illustrated by solving case studies from the literature. It is notable from these examples that considerable design flexibility exists in networks of this type, since potentially both the lean and reject streams from the partitioning regenerator can be reused/recycled within the plant.     

Metal accumulation in mosses across national boundaries: uncovering and ranking causes of spatial variation

This study aimed at cross-border mapping metal loads in mosses in eight European countries in 1990, 1995, and 2000 and at investigating confounding factors. Geostatistics was used for mapping, indicating high local variances but clear spatial autocorrelations. Inference statistics identified differences of metal concentrations in mosses on both sides of the national borders. However, geostatistical analyses did not ascertain discontinuities of metal concentrations in mosses at national borders due to sample analysis in different laboratories applying a range of analytical techniques. Applying Classification and Regression Trees (CART) to the German moss data as an example, the local variation in metal concentrations in mosses were proved to depend mostly on different moss species, potential local emission sources, canopy drip and precipitation.