Jason W. Birkett

Endocrine disrupters in wastewater and sludge treatment processes

Table of Contents SCOPE OF THE PROBLEM SOURCES OF ENDOCRINE DISRUPTERS METHODS FOR THE DETERMINATION OF ENDOCRINE DISRUPTERS FATE AND BEHAVIOUR OF ENDOCRINE DISRUPTERS IN WASTEWATER TREATMENT PROCESSES FATE AND BEHAVIOUR OF ENDOCRINE DISRUPTERS IN SLUDGE TREATMENT AND DISPOSAL ENDOCRINE DISRUPTERS IN RECEIVING WATERS ENDOCRINE DISRUPTERS IN DRINKING WATER AND WATER REUSE MANAGEMENT STRATEGIES FOR ENDOCRINE DISRUPTERS IN THE AQUATIC ENVIRONMENT

Analysis of Gunshot Residue and Associated Materials—A Review

Abstract:  A comprehensive review of the scientific literature on gunshot residue (GSR) is presented. Aspects of both inorganic and organic GSR are discussed, from formation and distribution, to sample collection, preparation, and analysis using a variety of techniques. The interpretation of GSR results is also considered including issues surrounding the contamination, distribution, and transfer of GSR. Potential problems with ulterior sources of GSR like particles have been reported in the literature. For example, particles from environmental and occupational sources have been highlighted as exhibiting similar chemical and morphological characteristics to GSR. These findings are put into context with regard to interpreting samples. A move toward a “case by case” approach is argued to be more preferable to a “formal” classification system where possible. The analysis of both inorganic and organic compositions of residue samples as well as morphological considerations is considered to be a more ideal approach to GSR analysis, whereever practicable.

Review of analytical techniques for arson residues

ABSTRACT: Arson is a serious crime that affects society through cost, property damage, and loss of life. It is important that the methods and technologies applied by fire investigators in detection of evidence and subsequent analyses have a high degree of reliability, sensitivity, and be subject to rigorous quality control and assurance. There have been considerable advances in the field of arson investigation since the 1950s. Classification of ignitable liquids has been updated to include many new categories due to developments in the petroleum industry. Techniques such as steam or vacuum distillation and gas chromatography (GC) with flame ionization detection that may have been considered acceptable—even a benchmark—40 years ago, are nowadays generally disfavored, to the extent that their implementation may almost be considered as ignorance in the field. The advent of readily available mass spectrometric techniques has revolutionized the field of fire debris analysis, increasing the degree of sensitivity and discrimination possible considerably. Multi‐dimensional GC—particularly GC × GC—while not yet widely applied, is rapidly gaining recognition as an important technique. This comprehensive review focuses on techniques and practices used in fire investigation, from scene investigation to analysis.

An assessment of the bioaccumulation of estrone in Daphnia magna

The bioaccumulation of estrone by Daphnia magna was determined. Direct uptake via the aqueous medium occurred within the first 16 h. A bioconcentration factor of 228 was established over all temporal periods. Ingestion via Chlorella vulgaris gave a partitioning factor of 24, which may approximate to a biomagnification factor assuming steady state conditions. These preliminary results indicate that the partitioning to Daphnia magna via the food source, C. vulgaris is less significant than bioconcentration.

Simultaneous determination of natural and synthetic steroid estrogens and their conjugates in aqueous matrices by liquid chromatography/mass spectrometry

An analytical method for the simultaneous determination of nine free and conjugated steroid estrogens was developed with application to environmental aqueous matrices. Solid-phase extraction (SPE) was employed for isolation and concentration, with detection by liquid chromatography/mass spectrometry (LC/MS) using electrospray ionisation (ESI) in the negative mode. Method recoveries for various aqueous matrices (wastewater, lake and drinking water) were determined, recoveries proving to be sample dependent. When spiked at 50 ng/L concentrations in sewage influent, recoveries ranged from 62–89% with relative standard deviations (RSD) <8.1%. In comparison, drinking water spiked at the same concentrations had recoveries between 82–100% with an RSD <5%. Ion suppression is a known phenomenon when using ESI; hence its impact on method recovery was elucidated for raw sewage. Both ion suppression from matrix interferences and the extraction procedure has a bearing on the overall method recovery. Analysis of municipal raw sewage identified several of the analytes of interest at ng/L concentrations, estriol (E3) being the most abundant. Only one conjugate, estrone 3-sulfate (E1-3S), was observed.

Spatial distribution of mercury in the sediments and riparian environment of the River Yare, Norfolk, UK.

Concentrations of total mercury (T-Hg) were determined in sediments and riparian (bankside) soils from the River Yare, Norfolk, UK to assess the current extent of contamination arising from a historical point source discharge. The results demonstrate that the spatial distribution pattern in surficial sediments and soils follows that of a distinct pollution plume with an initial increase 2-3 km downstream from the point source discharge at Whitlingham Sewage Treatment Works (STW) outfall. Average T-Hg concentrations in the surficial sediments ranged from 0.1 to 8.13 mg kg(-1); bankside soil concentrations ranged from 0.1 to 2.63 mg kg(-1). There has been a decline in downstream background sediment concentrations of Hg over time. This is likely to be the result of burial by fresh relatively uncontaminated sediments and possibly in the lower reach as a consequence of the influence of the freshwater-saline interface occurring near Cantley. Channel morphology was also shown to be an important factor in determining the large variations of Hg concentrations between sample points within transects. The predominant source of Hg to the soils appears to be due to dredging and the deposition of sediments during flooding.

Solid phase partitioning of metals in managed retreat soils: field changes over the first year of tidal inundation.

Sequential extraction methods were used to determine the effect of saline inundation on partitioning behaviour of metals in soils at Orplands Managed Retreat site, Essex, UK. A suite of metals (Al, Ca, Cr, Cu, Fe, K, Li, Mn, Ni, Pb and Zn) were analysed in sequential extracts from samples of soil cores extracted immediately before breaching of sea walls in 1995 and 1 year after. Generally, partitioning of most metals was dominated by associations with the residual fraction and an absence of associations with the exchangeable fraction indicating a relatively uncontaminated environment. Changes in partitioning were predominantly limited to the top 8 cm of the soil profile where a decaying mat of vegetation from the pre-inundation surface resulted in high moisture contents and low redox potentials. In this zone, the predominance of metal associations with the residual fraction was replaced by associations with more labile fractions. In the surface layer deposited after breaching, Ca was dominantly associated with the carbonate fraction, which indicates biogenic import from adjacent estuarine sediments.

The evaluation of solid phase micro-extraction fibre types for the analysis of organic components in unburned propellant powders

This work describes the evaluation of various solid phase micro-extraction (SPME) fibre types for the detection of compounds originating from particles of unburned propellant powders. These compounds may also be found in association with organic gunshot residues (OGSR). Seven SPME fibres were assessed based on their ability to extract the compounds of interest (diphenylamine (DPA), 4-nitrodiphenylamine (4-NDPA), ethyl centralite (EC), nitroglycerin (NG) and dibutyl phthalate (DBP)) from four ammunition types across three calibres (9 mm, 5.56 mm and 7.62 mm). Extracts were analysed by gas chromatography/mass spectrometry (GC/MS). Results indicated that the 65 μm polydimethylsiloxane/divinylbenzene (PDMS/DVB) was the most suitable fibre type for the extraction of these compounds across the ammunition types tested. Optimal extraction time parameters were also assessed with a 35-min period determined to be suitable. A number of previously unreported considerations for extracting propellant powders and potentially OGSR related materials are discussed.

Experimental determination of partial specific volumes of humic substances in aqueous solutions

Partial specific volume is an important molecular parameter in the measurement of molecular masses by analytical ultracentrifugation and X-ray diffraction studies. Humic substances (aquatic fulvic and humic acids and peat humic acid) were isolated from a natural source (Whitray Fell, UK). The partial specific volumes ( ) have been studied by two independent methods, an analytical ultracentrifugation technique based on simultaneous sedimentation equilibrium measurements in water and deuterium oxide and by high precision digital densimetry. Measurements were made in a range of conditions from 0.01 M to 0.5 M salt concentration and in the humic substance concentration range 0.01 to 2 mg ml−1. Partial specific volumes in the range 0.43 to 0.63 cm3 g−1 were found depending on the samples and conditions. No evidence was found for a dependence of ( ) on humic concentration within the ranges studied. Both methods of measurements gave results in reasonable accord. The ultracentrifugation method was more precise for the aquatic fulvic acid than for the more polydisperse humic acids. For the fulvic sample the reproducibility of the ultracentrifugation method was ± 4.31%, comparable to the average reproducibility of the densimetry method which was ± 4.07% over a range of 12 different systems.

Aggregation of humic substances by metal ions measured by ultracentrifugation

Abstract UV scanning analytical ultracentrifugation has been used to measure the aggregation of dissolved humic substances by metal ions. An adaptation of the Archibald approach to equilibrium technique has been used to monitor the change in average molecular weight, both with time, and also with mass of sample. The results have been analysed to give molecular weight distributions in the aggregated systems. For each metal studied, it was found that there was a threshold concentration below which no aggregation was observed, the magnitude of that concentration depending upon the metal. The range of concentrations from the onset of aggregation to the precipitation of the humic also depends upon the metal. It was found that the metal ions promoted aggregation in the order: La3+>Cu2+>Cd2+>Ag+. Tl4+, however, were found not to induce aggregation. In addition, the effects of ageing time, solution pH and ionic strength have been studied. It was also found that many of the aggregated humic populations were stable in solution for periods of weeks, and that the aggregation threshold concentration was independent of solution ionic strength. It was found that the aggregation was not the result of simple double layer compression as predicted by the Schulze-Hardy rule. Rather, the metal ions were reducing the intermolecular repulsion by reducing the humic charge.