The Status of Sanitation in Malawi: Is SDG6.2 Achievable?

Ensuring access to adequate and equitable sanitation and ending open defecation by 2030 is the focus of Sustainable Development Goal 6.2 (SDG6.2). We evaluated Malawi's progress towards SDG 6.2 (specifically the goal to end open defecation), presenting the results of a national survey of over 200,000 sanitary facilities and evaluating their management. Based on non-linear population dynamics, we used a linear model to evaluate the reduction in open defecation between 1992-2018, and to project whether Malawi can meet the SDG target to end open defecation by 2030 under multiple scenarios of population growth. Whilst Malawi has made considerable progress in providing sanitary provision for the population, we estimate that, at the current rate of the provision of sanitary facilities, Malawi will not reach SDG 6.2 by 2030 under any of the modelled socioeconomic scenarios. Furthermore, we compare the estimates of the extent of sanitary provision classed as improved from multiple surveys, including the USAID Demographic and Health (DHS) Surveys and Government of Malawi Census data. We conclude that some of the surveys (particularly the 2015/16 DHS) may be overestimating the level of improved sanitary provision, and we hypothesize that this is due to how pit-latrines with earth/sand slabs are classed. Furthermore, we examine the long-term sustainability of pit-latrine use, investigating the challenge of pit-latrine abandonment and identifying pit-latrine filling as a cause of the abandonment in 30.2% of cases. We estimate that between 2020-2070, 31.8 (range 2.8 to 3320) million pit-latrines will be filled and abandoned, representing a major challenge for the safe management of abandoned latrines, a potential for long-term impacts on the groundwater quality, and a significant loss of investment in sanitary infrastructure. For Malawi to reach SDG 6.2, improvements are needed in both the quantity and quality of its sanitary facilities.

Acute health risks to community hand-pumped groundwater supplies following Cyclone Idai flooding.

This longitudinal flood-relief study assessed the impact of the March 2019 Cyclone Idai flood event on E. coli contamination of hand-pumped boreholes in Mulanje District, Malawi. It established the microbiological water-quality safety of 279 community supplies over three phases, each comprising water-quality survey, rehabilitation and treatment verification monitoring. Phase 1 contamination three months after Idai was moderate, but likely underestimated. Increased contamination in Phase 2 at 9 months and even greater in Phase 3, a year after Idai was surprising and concerning, with 40% of supplies then registering E. coli contamination and 20% of supplies deemed 'unsafe'. Without donor support for follow-up interventions, this would have been missed by a typical single-phase flood-relief activity. Contamination rebound at boreholes successfully treated months earlier signifies a systemic problem from persistent sources intensified by groundwater levels likely at a decade high. Problem extent in normal, or drier years is unknown due to absence of routine monitoring of water point E. coli in Malawi. Statistical analysis was not conclusive, but was indicative of damaged borehole infrastructure and increased near-borehole pit-latrine numbers being influential. Spatial analysis including groundwater flow-field definition (an overlooked sector opportunity) revealed 'hit-and-miss' contamination of safe and unsafe boreholes in proximity. Hydrogeological control was shown by increased contamination near flood-affected area and in more recent recharge groundwater otherwise of good quality. Pit latrines are presented as credible e-coli sources in a conceptual model accounting for heterogeneous borehole contamination, wet season influence and rebound behavior. Critical to establish are groundwater level - flow direction, hand-pump plume draw, multiple footprint latrine sources - 'skinny' plumes, borehole short-circuiting and fast natural pathway (e.g. fracture flow) and other source influences. Concerted WASH (Water, Sanitation and Hygiene) sector investment in research and policy driving national water point based E. coli monitoring programs are advocated.

Fluoride occurrence in the lower East African Rift System, Southern Malawi.

Countries located on the East African Rift System (EARS) are vulnerable to fluoride in their groundwater; a vulnerability for the developing country of Malawi at the southern rift periphery that is not well characterised. Groundwater fluoride occurrence in Malawi is documented here to better understand and manage fluoride risks posed. Available literature and Gov't of Malawi archive fluoride data spanning some fifty years have been collated and augmented by our own 2016-18 surveys of groundwater quality in Southern Malawi, targeting deep-sourced springs. In total, fluoride data for 1365 borehole, spring and hot spring samples were assembled. Statistically, 83% of samples were below the 1.5 mg/l WHO limit, concentrations in the 1.5-6 mg/l range between former (pre-1993) and current WHO guidelines at 14%, and those with fluoride above the current Malawi (former WHO) 6 mg/l guideline, at 3%. A lower occurrence than in other zones of the EARS, but indicative of a need for a Malawi Gov't management policy revision and associated management strategies endorsed by several documented incidences of dental fluorosis in proximity to high fluoride groundwater. Increased fluoride is related to increased groundwater temperatures signifying the importance of geothermal groundwater provenance. Temperature data may indeed be used as a proxy indicator of fluoride risk; samples with a temperature >32 °C, contained >6 mg/l fluoride. Structural geological controls appear to allow deep geothermal groundwaters to come to the near surface, as evidenced by increased fluoride in springs and boreholes close to faulted areas. Hydrochemical evaluation shows that fluoride concentrations are influenced by fluorite equilibration and sensitivity to calcium and pH. Recommendations are made to further document the occurrence of fluoride and enhance management of risks due to fluoride in drinking water in Malawi. With fluoride as a key indicator within Sustainable Development Goal number 6, the current Malawi standard and waters with concentration between 1.5 and 6 mg/l will come under increased scrutiny and pose a key challenge to assessment and management efforts.

A comprehensive optimum integrated water resources management approach for multidisciplinary water resources management problems.

A holistic Integrated Water Resources Management (IWRM) model can be difficult to implement and the associated high-dimension optimization problems' complexity often forces the decision makers to downscale such problems. These challenges however have motivated this research to develop a comprehensive Optimum IWRM approach (OP-IWRM) using a many-objective optimization algorithm to solve complex and large-scale problems. The approach employs the social, economic, and environmental objectives; ground and surface water resources; and water infrastructure for river basin management to: (1) improve the relevant revenues, (2) enhance community welfare, and (3) pave the road for the decision makers to set better investment policy. The results demonstrate comprehensive improvement of all considered targets. The decision makers may reconsider implementing complex integrated water resources management of large-scale regions. The OP-IWRM may extend for country-scale approach as a pathway towards a national sustainable development plan. The large-scale Diyala river basin, Iraq, was adopted to evaluate the approach using seventeen objectives and more than 1500 decision variables.

Responding to salinity in a rural African alluvial valley aquifer system: To boldly go beyond the world of hand-pumped groundwater supply?

Effective response to groundwater salinity in the developing world may critically safeguard drinking-water supplies. Groundwater resources throughout rural Africa are exploited by a vast and increasing number of hand-pumped boreholes for community supply. Our research in TA Ngabu (Shire Valley), Southern Malawi aims to: define groundwater-salinity problem occurrence within the semi-arid alluvial-valley aquifer, rural developing-world setting; critique current capacity to respond; and, to discuss future response options - in particular considering the need to explore alternative options that boldly go beyond the world of hand-pumped groundwater supply. Salinity problem definition was achieved through survey of 419 hand-pumped boreholes that revealed widespread brackish groundwater leading to non-potable (unpalatable) drinking-water supplies. Persistent non-functionality or abandonment of boreholes was typically ascribed to salinity. Whilst salinity is conceptualised to arise from shallow-groundwater evaporation, formation-evaporite dissolution and faulted-area upwelling, sparse data locally renders attribution of salinity sources to individual boreholes difficult. There is a significant need to better resolve the vertical distribution of salinity and local controlling processes. Problem response capacity was hampered by multiple factors, including, sector inertia, low drilling costs compromising water-point integrity, and lack of technical vision for alternatives. Various recommendations are made to improve response capacity continuing to work at the hand-pump supply scale. However, in areas where salinity is significant, exploring the feasibility of other options is advocated in conjunction with technical capacity development. Groundwater options may utilise high borehole yields possible from alluvial aquifers, grossly under-exploited by hand pumps. Groundwater at depth, albeit of unknown quality typically, or pipeline transfers of probable good-quality groundwater from valley-margin units, should be considered. Surface-water pipeline supplies may be viable for (growing) population centres. Canal-fed irrigation schemes (pending for the area), should be multiple-use, protective of groundwater and embrace pipeline drinking-water supply and managed-aquifer-recharge opportunities. Advancing desalination technologies, although presently unaffordable, should be kept under review.

Performance of a field-scale biological permeable reactive barrier for in-situ remediation of nitrate-contaminated groundwater.

We report the performance of a field-scale permeable reactive barrier (PRB) for the biological treatment of nitrate-contaminated groundwater. The reactive material of the PRB consisted of a mixture of gravel and mulch as a carbon source for denitrifying bacteria. The PRB was equipped with a delivery system that allowed injecting NO3- at controlled rates from the surface directly into the up-gradient layer of the PRB. This way, NO3- concentration entering the PRB was varied (from 1 to 530 mg/L) with the purpose of evaluating the ultimate efficiency of the PRB under different NO3- loadings. The PRB was successful at removing NO3- from groundwater at inlet concentrations up to 280 mg/L (with NO3- removal percentages ≥97%). Monitoring of groundwater at different depths within the PRB provided evidence that NO3- underwent denitrification preferably at the deepest part of the PRB, where more favourable reducing conditions were achieved. Among the shortcomings of the PRB were the fluctuations of groundwater fluxes caused by intense rainfalls during the study period, although they generally did not pose concern for the denitrification capacity of the PRB. Emission fluxes of gases (CO2, CH4 and N2O) from the PRB to the atmosphere were also measured. The results are finally compared with the few others reported existing PRBs for nitrate-contaminated groundwater worldwide.

Optimum socio-environmental flows approach for reservoir operation strategy using many-objectives evolutionary optimization algorithm.

Water resource system complexity, high-dimension modelling difficulty and computational efficiency challenges often limit decision makers' strategies to combine environmental flow objectives (e.g. water quality, ecosystem) with social flow objectives (e.g. hydropower, water supply and agriculture). Hence, a novel Optimum Social-Environmental Flows (OSEF) with Auto-Adaptive Constraints (AAC) approach introduced as a river basin management decision support tool. The OSEF-AAC approach integrates Socio-Environmental (SE) objectives with convergence booster support to soften any computational challenges. Nine SE objectives and 396 decision variables modelled for Iraq's Diyala river basin. The approach's effectiveness evaluated using two non-environmental models and two inflows' scenarios. The advantage of OSEF-AAC approved, and other decision support alternatives highlighted that could enhance river basin SE sectors' revenues, as river basin economic benefits will improve as well. However, advanced land use and water exploitation policy would need adoption to secure the basin's SE sectors.

Local scale water-food nexus: Use of borehole-garden permaculture to realise the full potential of rural water supplies in Malawi.

Local-scale opportunities to address challenges of the water-food nexus in the developing world need to be embraced. Borehole-garden permaculture is advocated as one such opportunity that involves the sustainable use of groundwater spilt at hand-pump operated borehole supplies that is otherwise wasted. Spilt water may also pose health risks when accumulating as a stagnant pond. Rural village community use of this grey-water in permaculture projects to irrigate borehole gardens is proposed to primarily provide economic benefit whereby garden-produce revenue helps fund borehole water-point maintenance. Water-supply sustainability, increased food/nutrition security, health protection from malaria, and business opportunity benefits may also arise. Our goal has been to develop an, experience-based, framework for delivery of sustainable borehole-garden permaculture and associated benefits. This is based upon data collection and permaculture implementation across the rural Chikwawa District of Malawi during 2009-17. We use, stakeholder interviews to identify issues influencing uptake, gathering of stagnant pond occurrence data to estimate amelioration opportunity, quantification of permaculture profitability to validate economic potential, and critical assessment of recent permaculture uptake to identify continuing problems. Permaculture was implemented at 123 sites representing 6% of District water points, rising to 26% local area coverage. Most implementations were at, or near, newly drilled community-supply boreholes; hence, amelioration of prevalent stagnant ponds elsewhere remains a concern. The envisaged benefits of permaculture were manifest and early data affirm projected garden profitability and spin-off benefits of water-point banking and community micro-loan access. However, a diversity of technical, economic, social and governance issues were found to influence uptake and performance. Example issues include greater need for improved bespoke garden design input, on-going project performance assessment, and coordinated involvement of multi-sector governmental-development bodies to underpin the integrated natural-resource management required. The developed framework aims to manage the identified issues and requires the concerted action of all stakeholders. Based on the probable ubiquity of underlying issues, the framework is expected to be generalizable to the wider developing world. However, this particular application of permaculture represents a fraction of its greater potential opportunity for rural communities that should be explored.

Risk assessment to groundwater of pit latrine rural sanitation policy in developing country settings.

Parallel global rise in pit-latrine sanitation and groundwater-supply provision is of concern due to the frequent spatial proximity of these activities. Study of such an area in Malawi has allowed understanding of risks posed to groundwater from the recent implementation of a typical developing-country pit-latrine sanitation policy to be gained. This has assisted the development of a risk-assessment framework approach pragmatic to regulatory-practitioner management of this issue. The framework involves water-supply and pit-latrine mapping, monitoring of key groundwater contamination indicators and surveys of possible environmental site-condition factors and culminates in an integrated statistical evaluation of these datasets to identify the significant factors controlling risks posed. Our approach usefully establishes groundwater-quality baseline conditions of a potentially emergent issue for the study area. Such baselines are foundational to future trend discernment and contaminant natural attenuation verification critical to policies globally. Attribution of borehole contamination to pit-latrine loading should involve, as illustrated, the use of the range of contamination (chemical, microbiological) tracers available recognising none are ideal and several radial and capture-zone metrics that together may provide a weight of evidence. Elevated, albeit low-concentration, nitrate correlated with some radial metrics and was tentatively suggestive of emerging latrine influences. Longer term monitoring is, however, necessary to verify that the commonly observed latrine-borehole separation distances (29-58m), alongside statutory guidelines, do not constitute significant risk. Borehole contamination was limited and correlation with various environmental-site condition factors also limited. This was potentially ascribed to effectiveness of attenuation to date, monitoring of an emergent problem yet to manifest, or else contamination from other sources. High borehole usage and protective wall absence correlated with observed microbiological contamination incidence, but could relate to increased human/animal activity close to these poorly protected boreholes. Additional to factors assessed, a groundwater-vulnerability factor is recommended that critically relies upon improved proactive securing of underpinning data during borehole/latrine installations. On-going concerns are wide ranging, including poorly constrained pit-latrine input, difficulties in assessing in-situ plume natural attenuation and possible disposal of used motor oils to latrines.

Comprehensive database of Manufactured Gas Plant tars. Part B. Aliphatic and aromatic compounds.

RATIONALE: Coal tars are a mixture of organic and inorganic compounds that were produced as a by-product from the manufactured gas and coke making industries. The composition of the tar produced varies depending on many factors; these include the temperature of production and the type of retort used. As different production processes produce different tars, a comprehensive database of the compounds present within coal tars from different production processes is a valuable resource. Such a database would help to understand how their chemical properties differ and what hazards the compounds present within these tars might pose. This study focuses on the aliphatic and aromatic compounds present in a database of 16 different tars from five different production processes. METHODS: Samples of coal tar were extracted using accelerated solvent extraction (ASE) and derivatised post-extraction using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) with 1% trimethylchlorosilane (TMCS). The derivatised samples were analysed using two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GCxGC/TOFMS). RESULTS: A total of 198 individual aliphatic and 951 individual aromatic compounds were detected within 16 tar samples produced by five different production processes. The polycyclic aromatic hydrocarbon (PAH) content of coal tars varies greatly depending on the production process used to obtain the tars and this is clearly demonstrated within the results. The aliphatic composition of the tars provided an important piece of analytical information that would have otherwise been missed with the detection of petrogenic compounds such as alkyl cyclohexanes. CONCLUSIONS: The aromatic compositions of the tar samples varied greatly between the different production processes investigated and useful analytical information was obtained about the individual production process groups. Alkyl cyclohexanes were detected in all samples from sites known to operate Carbureted Water Gas plants and not detected in those that did not. This suggests that petrogenic material may be expected at many UK gaswork sites.

Comprehensive database of Manufactured Gas Plant tars. Part A. Database.

RATIONALE: Coal tars are a mixture of organic and inorganic compounds that were by-products from the manufactured gas and coke making industries. Different manufacturing processes have resulted in the production of distinctly different tar compositions. This study presents a comprehensive database of compounds produced using two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GCxGC/TOFMS), analysing 16 tar samples produced by five distinct production processes. METHODS: Samples of coal tar were extracted using accelerated solvent extraction (ASE) and derivatised post-extraction using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) with 1% trimethylchlorosilane (TMCS). The derivatised samples were analysed using two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GCxGC/TOFMS). RESULTS: A total of 16 tar samples originating from five different production processes: Low Temperature Horizontal Retorts, Horizontal Retorts, Vertical Retorts, Carbureted Water Gas and Coke Ovens, were analysed. A total of 2369 unique compounds were detected with 948 aromatic compounds, 196 aliphatic compounds, 380 sulfur-containing compounds, 209 oxygen-containing compounds, 262 nitrogen-containing compounds and 15 mixed heterocycles. Derivatisation allowed the detection of 359 unique compounds, the majority in the form of hydroxylated polycyclic aromatic hydrocarbons, many of which would not have been detected without derivatisation. Of the 2369 unique compounds detected, 173 were found to be present within all samples. CONCLUSIONS: A unique comprehensive database of compounds detected within 16 tar samples from five different production processes was produced. The 173 compounds identified within every sample may be of particular importance from a regulatory standpoint. This initial study indicates that different production processes produce tars with different chemical signatures and it can be further expanded upon by in-depth analysis of the different compound types. The number of compounds presented within this database clearly demonstrates the analytical power of GCxGC/TOFMS.

Comprehensive database of Manufactured Gas Plant tars. Part C. Heterocyclic and hydroxylated polycyclic aromatic hydrocarbons.

RATIONALE: Coal tars are a mixture of organic and inorganic compounds that were by-products from the manufactured gas and coke making industries. The tar compositions varied depending on many factors such as the temperature of production and the type of retort used. For this reason a comprehensive database of the compounds found in different tar types is of value to understand both how their compositions differ and what potential chemical hazards are present. This study focuses on the heterocyclic and hydroxylated compounds present in a database produced from 16 different tars from five different production processes. METHODS: Samples of coal tar were extracted using accelerated solvent extraction (ASE) and derivatized post-extraction using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) with 1% trimethylchlorosilane (TMCS). The derivatized samples were analysed using two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GCxGC/TOFMS). RESULTS: A total of 865 heterocyclic compounds and 359 hydroxylated polycyclic aromatic hydrocarbons (PAHs) were detected in 16 tar samples produced by five different processes. The contents of both heterocyclic and hydroxylated PAHs varied greatly with the production process used, with the heterocyclic compounds giving information about the feedstock used. Of the 359 hydroxylated PAHs detected the majority would not have been be detected without the use of derivatization. CONCLUSIONS: Coal tars produced using different production processes and feedstocks yielded tars with significantly different heterocyclic and hydroxylated contents. The concentrations of the individual heterocyclic compounds varied greatly even within the different production processes and provided information about the feedstock used to produce the tars. The hydroxylated PAH content of the samples provided important analytical information that would otherwise not have been obtained without the use of derivatization and GCxGC/TOFMS.

Comprehensive composition of Creosote using comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GCxGC-TOFMS).

Creosote is a distillation product of coal tar and is widely used as wood preservative for railway sleepers, utility poles and for other applications. Creosote can have potentially negative effects on the environment and many of the components are toxic. This study presents the analysis of a Creosote sample from a former wood impregnation plant located in the UK. The sample was analysed using two dimensional gas chromatography time-of-flight mass spectrometry (GCxGC-TOFMS) and a database of compounds that could be detected was produced. The GCxGG-TOFMS was capable of detecting 1505 individual compounds, which is far more than previous estimates for the number of compounds present within Creosote. Post extraction derivatization using BTSFA with 1% TMCS was employed to increase the potential number of compounds detected with 255 derivatized compounds detected, 231 of which would not have been detected without prior derivatization. Selected derivatized compounds were quantified with limits of detection ranging from 0.6 mg/kg to 1.6 mg/kg from a concentrated dense non-aqueous phase liquid (DNAPL). This work presents the first published full analysis of a Creosote using GCxGC-TOFMS combined with derivatization.

Frequency-dependent ultrasound-induced transformation in E. coli.

Ultrasound-enhanced gene transfer (UEGT) is continuing to gain interest across many disciplines; however, very few studies investigate UEGT efficiency across a range of frequencies. Using a variable frequency generator, UEGT was tested in E. coli at six ultrasonic frequencies. Results indicate frequency can significantly influence UEGT efficiency positively and negatively. A frequency of 61 kHz improved UEGT efficiency by ~70 % higher, but 99 kHz impeded UEGT to an extent worse than no ultrasound exposure. The other four frequencies (26, 133, 174, and 190 kHz) enhanced transformation compared to no ultrasound, but efficiencies did not vary. The influence of frequency on UEGT efficiency was observed across a range of operating frequencies. It is plausible that frequency-dependent dynamics of mechanical and chemical energies released during cavitational-bubble collapse (CBC) are responsible for observed UEGT efficiencies.

Environmental and toenail metals concentrations in copper mining and non mining communities in Zambia.

Copper mining contributes to increased concentrations of metals in the environment, thereby increasing the risk of metals exposure to populations living in and around mining areas. This study investigated environmental and toenail metals concentrations of non-occupational human exposure to metals in 39 copper-mining town residents and 47 non-mining town residents in Zambia. Elevated environmental concentrations were found in samples collected from the mining town residents. Toenail concentrations of cobalt (GM 1.39 mg/kg), copper (GM 132 mg/kg), lead (21.41 mg/kg) selenium (GM 0.38 mg/kg) and zinc (GM 113 mg/kg) were significantly higher in the mining area and these metals have previously been associated with copper mining. Residence in the mining area, drinking water, dust and soil metals concentrations were the most important contributors to toenail metals concentrations. Further work is required to establish the specific pathways of exposure and the health risks of elevated metals concentrations in the copper mining area.

A culture-independent approach to unravel uncultured bacteria and functional genes in a complex microbial community.

Most microorganisms in nature are uncultured with unknown functionality. Sequence-based metagenomics alone answers 'who/what are there?' but not 'what are they doing and who is doing it and how?'. Function-based metagenomics reveals gene function but is usually limited by the specificity and sensitivity of screening strategies, especially the identification of clones whose functional gene expression has no distinguishable activity or phenotypes. A 'biosensor-based genetic transducer' (BGT) technique, which employs a whole-cell biosensor to quantitatively detect expression of inserted genes encoding designated functions, is able to screen for functionality of unknown genes from uncultured microorganisms. In this study, BGT was integrated with Stable isotope probing (SIP)-enabled Metagenomics to form a culture-independent SMB toolbox. The utility of this approach was demonstrated in the discovery of a novel functional gene cluster in naphthalene contaminated groundwater. Specifically, metagenomic sequencing of the (13)C-DNA fraction obtained by SIP indicated that an uncultured Acidovorax sp. was the dominant key naphthalene degrader in-situ, although three culturable Pseudomonas sp. degraders were also present in the same groundwater. BGT verified the functionality of a new nag2 operon which co-existed with two other nag and two nah operons for naphthalene biodegradation in the same microbial community. Pyrosequencing analysis showed that the nag2 operon was the key functional operon in naphthalene degradation in-situ, and shared homology with both nag operons in Ralstonia sp. U2 and Polaromonas naphthalenivorans CJ2. The SMB toolbox will be useful in providing deep insights into uncultured microorganisms and unravelling their ecological roles in natural environments.

Multivariate statistical methods for the environmental forensic classification of coal tars from former manufactured gas plants.

Compositional disparity within a set of 23 coal tar samples (obtained from 15 different former manufactured gas plants) was compared and related to differences between historical on-site manufacturing processes. Samples were prepared using accelerated solvent extraction prior to analysis by two-dimensional gas chromatography coupled to time-of-flight mass spectrometry. A suite of statistical techniques, including univariate analysis, hierarchical cluster analysis, two-dimensional cluster analysis, and principal component analysis (PCA), were investigated to determine the optimal method for source identification of coal tars. The results revealed that multivariate statistical analysis (namely, PCA of normalized, preprocessed data) has the greatest potential for environmental forensic source identification of coal tars, including the ability to predict the processes used to create unknown samples.

Carbon isotopic fractionation of CFCs during abiotic and biotic degradation.

Carbon stable isotope ((13)C) fractionation in chlorofluorocarbon (CFC) compounds arising from abiotic (chemical) degradation using zero-valent iron (ZVI) and biotic (landfill gas attenuation) processes is investigated. Batch tests (at 25 °C) for CFC-113 and CFC-11 using ZVI show quantitative degradation of CFC-113 to HCFC-123a and CFC-1113 following pseudo-first-order kinetics corresponding to a half-life (τ(1/2)) of 20.5 h, and a ZVI surface-area normalized rate constant (k(SA)) of -(9.8 ± 0.5) × 10(-5) L m(-2) h(-1). CFC-11 degraded to trace HCFC-21 and HCFC-31 following pseudo-first-order kinetics corresponding to τ(1/2) = 17.3 h and k(SA) = -(1.2 ± 0.5) × 10(-4) L m(-2) h(-1). Significant kinetic isotope effects of ε(‰) = -5.0 ± 0.3 (CFC-113) and -17.8 ± 4.8 (CFC-11) were observed. Compound-specific carbon isotope analyses also have been used here to characterize source signatures of CFC gases (HCFC-22, CFC-12, HFC-134a, HCFC-142b, CFC-114, CFC-11, CFC-113) for urban (UAA), rural/remote (RAA), and landfill (LAA) ambient air samples, as well as in situ surface flux chamber (FLUX; NO FLUX) and landfill gas (LFG) samples at the Dargan Road site, Northern Ireland. The latter values reflect biotic degradation and isotopic fractionation in LFG production, and local atmospheric impact of landfill emissions through the cover. Isotopic fractionations of Δ(13)C ∼ -13‰ (HCFC-22), Δ(13)C ∼ -35‰ (CFC-12) and Δ(13)C ∼ -15‰ (CFC-11) were observed for LFG in comparison to characteristic solvent source signatures, with the magnitude of the isotopic effect for CFC-11 apparently similar to the kinetic isotope effect for (abiotic) ZVI degradation.

Simplifying and improving the extraction of nitrate from freshwater for stable isotope analyses.

Determining the isotopic composition of nitrate (NO(3)(-)) in water can prove useful to identify NO(3)(-) sources and to understand its dynamics in aquatic systems. Among the procedures available, the 'ion-exchange resin method' involves extracting NO(3)(-) from freshwater and converting it into solid silver nitrate (AgNO(3)), which is then analysed for (15)N/(14)N and (18)O/(16)O ratios. This study describes a simplified methodology where water was not pre-treated to remove dissolved organic carbon (DOC) or barium cations (added to precipitate O-bearing contaminants), which suited samples with high NO(3)(-) (≥ 00 µM or 25 mg L(-1) NO(3)(-)) and low DOC (typically < 17 µM of C or 5 mg L(-1) C) levels. % N analysis revealed that a few AgNO(3) samples were of low purity (compared with expected % N of 8.2), highlighting the necessity to introduce quality control/quality assurance procedures for silver nitrate prepared from field water samples. Recommendations are then made to monitor % N together with % O (expected at 28.6, i.e. 3.5 fold % N) in AgNO(3) in order to better assess the type and gravity of the contamination as well as to identify potentially unreliable data.

Ultra resolution chemical fingerprinting of dense non-aqueous phase liquids from manufactured gas plants by reversed phase comprehensive two-dimensional gas chromatography.

Ultra resolution chemical fingerprinting of dense non-aqueous phase liquids (DNAPLs) from former manufactured gas plants (FMGPs) was investigated using comprehensive two-dimensional gas chromatography coupled with time of flight mass spectrometry (GC×GC TOFMS). Reversed phase GC×GC (i.e. a polar primary column coupled to a non-polar secondary column) was found to significantly improve the separation of polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologues. Sample extraction and cleanup was performed simultaneously using accelerated solvent extraction (ASE), with recovery rates between 76% and 97%, allowing fast, efficient extraction with minimal solvent consumption. Principal component analysis (PCA) of the GC×GC data was performed in an attempt to differentiate between twelve DNAPLs based on their chemical composition. Correlations were discovered between DNAPL composition and historic manufacturing processes used at different FMGP sites. Traditional chemical fingerprinting methods generally follow a tiered approach with sample analysis on several different instruments. We propose ultra resolution chemical fingerprinting as a fast, accurate and precise method of obtaining more chemical information than traditional tiered approaches while using only a single analytical technique.