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The legacy of chlorinated solvents in groundwater:an overlooked 1940s contribution

Dr Michael Rivett
University of Birmingham
m.o.rivett@bham.ac.uk 
ECB Bulletin January 2010
Introduction
Industrial chlorinated solvents have become widespread pollutants of groundwater. General awareness of the solvents-in-groundwater problem emerged in the 1970-80s, some 50 years after the onset of their industrial use. By this time large amounts of solvent had been used, and disposed of, with poor environmental awareness. The legacy of subsurface solvent pollution may be substantial, persistent, subject to legal action, and very costly to remediate. Interestingly, two members of the Royal Society of Chemistry, Frances Lyne and Thomas McLachlan, published a short paper in 1949 about solvent pollution of groundwater wells. Unfortunately, it appears their work has been largely overlooked by the scientific community.
The solvents-in-groundwater problem The apportionment of legal liability in cases of land and groundwater pollution may depend upon an alleged polluter’s awareness of an incident, and whether they could have reasonably foreseen the adverse consequences of their actions. In assessing foreseeability, one consideration is the published information at the time of pollutant release to determine whether there was a general recognition that the activities may have reasonably been foreseen to cause contamination problems. Historic cases of groundwater contamination are hence important in this regard. A short paper by Lyne and McLachlan (1949) has recently resurfaced from the literature describing historic cases of the now notorious groundwater pollutant trichloroethene (TCE, trichloroethylene, Cl2C=CHCl). This paper is believed to be the earliest journal publication worldwide on this class of environmental pollutant. It is hence important, and has been the subject of recent publications and debate (Colten & Skinner, 1994, 1996; Rivett et al., 2006; Rivett & Clark, 2007; Amter & Ross, 2008; Rivett 2008). A review of that interest, based largely on Rivett et al. (2006) and Rivett (2008), is presented in this article.
By the mid to late 1980s, it was clear internationally that chlorinated solvents, for example trichloroethene, 1,1,1-trichloroethane (TCA, Cl3CCH3), and tetrachloroethene (perchloroethylene, PCE, Cl2C=CCl2), were very prevalent groundwater contaminants (Mackay and Cherry, 1989; Schaumburg, 1990; Rivett et al., 1990). Chlorinated solvents, typically C1-C2 chlorinated aliphatic hydrocarbon (CAH) alkenes/alkanes, have been used widely by industry since the 1920-30s (Rivett et al., 1990), often as a general purpose degreaser. TCE was extensively used in metal fabrication and engineering, PCE in textile and leather degreasing and TCA in circuit-board manufacturing (Pankow et al., 1996). ICI (Imperial Chemical Industries plc) has been the UK’s principal manufacturer at its Runcorn plant. Limited quantities of TCE were produced until 1927 when suitable degreasing containers were developed, resulting in UK productivity expanding to ca. 40,000 tons p.a. by 1949 and peaking at ca. 90,000 tons in 1970 (Rivett et al., 1990). Shortly after this peak, the chronic carcinogenicity of TCE was recognised in 1975 (NIOSH, 1975). This led to low µg/L drinking-water standards being established, reduced TCE/PCE production, and some replacement by TCA until the latter’s atmospheric pollution potential was recognised. Acute health effects from occupational exposure to TCE have been known since the 1930s (Stuber, 1932).
Chlorinated solvents are a challenging groundwater problem for a variety of reasons. They are dense non-aqueous phase liquids (DNAPLs) that are immiscible with water, but still sufficiently soluble to exceed drinking-water standards by several orders of magnitude. Their denser-than-water nature combined with their low viscosity may permit very rapid penetration of DNAPL solvents far below the water table in many aquifers (Mackay and Cherry, 1989). Often the recommended practice for disposal of used solvents, up until the 1970s and perhaps beyond, was to pour solvents onto the ground (or pits) to allow solvents to evaporate – with or without ignition; there was significant potential for rapid infiltration of solvent DNAPL into the subsurface.  Such disposal practices and inadvertent spillages have led to many DNAPL sources being present in aquifers, often at depths where other pollutants may never reach. Such DNAPL may typically persist for decades (Rivett & Feenstra, 2005) and slowly dissolve to yield persistent groundwater plumes that can extend up to kilometre scales and more (Jackson 1998). There have been many high-profile sites, some with contentious legal cases that can involve tens and in some cases millions of dollars of site investigation and remediation works (Misstear, 1998; Kirtland et al., 2003; Oostrom et al., 2007).
Lyne & McLachlan (1949)
Some 60 years ago, two UK chemists, Lyne and McLachlan, published “Contamination of water by trichloroethylene” (Lyne & McLachlan, 1949). Their entire paper is reproduced in Figure 1 and was originally published in the journal The Analyst. Despite its brevity, the paper has significant content. Two separate cases of groundwater wells contaminated by TCE are described, arising from a tank release and a suspected leaking disposal-pit. Human-health effects are reported, e.g. stomach disorders, giddiness. A colorimetric method of analysis was described to quantify TCE concentrations in water. A concentration of 18 mg/L TCE in groundwater from a supply well was recorded (the first measurement worldwide) that exceeds current drinking water standards by a thousand-fold. A perceptive conclusion was reached: “that contamination by compounds of this nature is likely to be very persistent”; a conclusion that is all too evident nowadays.  As noted by Travis (1998), their conclusions were certainly worthy of more than passing notice, particularly since they drew attention to the threat to human health. Also, as explored by Rivett et al. (2006), in terms of wider liability and foreseeability, a fundamental question is – did Lyne and McLachlan (1949) trigger any recognition of the problem of groundwater contamination by TCE, or similar chlorinated solvents, at either a local, national or international level?
Picture
Figure 1. Manuscript of Lyne and McLachlan (1949). The Analyst, 1949, 74(882), 513, DOI: 10.1039/AN9497400510 – Reproduced by permission of the Royal Society of Chemistry. This article is available as part of the Royal Society of Chemistry Journals Archive at www.rsc.org/archive
Frances A. Lyne and Thomas McLachlan
Little information is given in the publication (Figure 1) concerning the authors, whose affiliations were disclosed as “Abbey Gateway, Reading”. Lyne and McLachlan were both members of the Royal Society of Chemistry (RSC) (and some of the constituent societies of the RSC before the amalgamation in 1980*). The RSC confirms that Mr Frances Arthur Lyne was born in 1913, died in 1996 and was a member of the RSC from 1934 until his death aged 83 years. Mr Thomas McLachlan was born in 1894, died in 1991 and was a member of the RSC from 1917 until his death aged 97 years. Although Lyne and McLachlan both lived into the 1990s and hence beyond the general 1970-80s period of recognition of the solvents-in-groundwater problem, there unfortunately appears to have been no detailed consultation with them concerning their 1949 paper before their deaths.

‘The County Borough’ section of the 1941 Nov. issue of The Reading Mercury indicates

“Mr Thomas McLachlan FIC of …  London … has been appointed …. as public and agricultural analyst for the County of Berkshire. He is to open a laboratory in Reading, and it is understood that he will act in a similar capacity for the Borough”
.

Analysts were officially appointed and authorised to provide certified (chemical) analyses. The Kelly’s Directory of Reading 1949 indicates:

“Public Analysts: Thomas McLachlan ACGFC FRIC (& Official Agricultural Chemist) & Frances Arthur Lyne FRIC, Abbey Gateway, Abbey St. Listed under ‘Officers of the Corporation and Urban Sanitary Authority’ so employed in that capacity by the Borough of Reading.”


The same directory also lists Thomas McLachlan as

“County Analyst (Food & Drugs & Fertilisers & Feeding Stuffs Acts)”


at the same address.  Part of an obituary by Lyne (1992) on McLachlan published in Chemistry in Britain confirms the above and more:

“During World War II McLachlan’s laboratory in central London was badly damaged but he moved to various locations including the Pharmaceutical Society in Bloomsbury Square. He showed great fortitude and tenacity in carrying on his professional work in spite of adversity resulting from enemy action. In 1942 McLachlan was appointed public analyst for Berkshire and the City of Oxford, and in partnership with F.A. Lyne opened a laboratory in Reading, in addition to his London laboratory.”


Travis (1998) further summarises Lyne and McLachlan’s public analyst appointments. He notes that in the late 1930s Lyne was the Public Analyst for Chelsea and authored 1941-42 public analyst reports for Fulham. In 1949 both Lyne and McLachlan gained Public Analyst responsibilities for Windsor (Berkshire) and Oxford, and McLachlan was also appointed Public Analyst for Thurrock, Essex. McLachlan was a founder member of the Association of Public Analysts.
The Reading address was primarily connected with their Public Analyst responsibilities for the Borough of Reading and for the wider County of Berkshire of which Reading is the County Town. In relation to the Reading/Berkshire positions, McLachlan was appointed around late 1941 and was still County Analyst in 1964 (aged 70). Lyne was still in his post as Public Analyst at least until 1975 (aged 62). Their 1940s laboratory was in Abbey Gateway, Abbey Street, Reading. This was located near the main entrance to the old Abbey near the centre of Reading (Figure 2). It is probable they had a floor of the present Crown Court, then predominantly the Berkshire County Police Headquarters. Lyne remained professionally involved into his 70s. Lyne headed the Lyne, Martin & Radford Public Analyst – a commercial laboratory based in Reading. Martin was a Public Analyst colleague of Lyne’s for several decades and was later joined by Radford.
Picture
Figure 2. The Abbey Gateway in Reading, Berkshire (2004) where Lyne and McLachlan’s laboratory was located in 1949 [from the address given in Lyne & McLachlan (1949)]
The case study sites
Significant effort was made by Rivett & Clark (2007) to locate the unidentified case-study sites described by Lyne & McLachlan through archive records, consultations with relevant professionals and field reconnaissance of the Reading area. Some potential sites were identified. However, none could be confirmed.  This is ascribed to the brief descriptions given in the paper, the lack of relevant historic record keeping and the relatively wide pre-1949 jurisdictional area covered by Lyne and McLachlan. It is more probable, although not proven, that the sites were located in the Reading area based upon:
  • the Reading address where they worked in 1949;        
  • the industrialized urban nature of this location;
  • the area contained a significant density of small-medium engineering works with war-time aircraft manufacture prominent (e.g. at least four aircraft-related sites in central Reading with the Miles Aircraft main factory on the outskirts at the Woodley aerodrome site);
  • the hydrogeology of the region – the Thames Valley gravel aquifer along with three main rivers.
However, failure to locate these sites today does not detract from the significance of Lyne and McLachlan’s paper.

Influences of Lyne and McLachlan (1949)
The relevance and influence of any published paper is subjective with different views possible. This is the case for Lyne and McLachlan (1949) as set out in the discussion (Amter & Ross, 2008) and reply (Rivett, 2008) to Rivett et al. (2006). The influence of Lyne and McLachlan (1949) may be considered under various headings: literature citations of Lyne and McLachlan (1949) from the scientific, technical and legal case literature and records; Lyne and McLachlan’s later careers and publications; local, national and international recognition of the ‘solvents-in-groundwater’ problem; and use of the analytical method described in their paper.

Literature citations to ‘Lyne and McLachlan’
General recognition of the solvents-in-groundwater problem began from the mid-to-late 1970s to 1980s (Pankow et al., 1996). This was some twenty-five years or more after Lyne and McLachlan’s 1949 publication and suggests that the influence of their work was limited. Citations of Lyne and McLachlan prior to ca.1980 are the most relevant to assessing the paper’s influence on problem recognition. It is always difficult to assure complete coverage of citing works, particularly of the grey literature, and indeed Amter & Ross (2008) add to those citations indicated by Rivett et al. (2006) with further response to those provided by Rivett (2008).

Lyne & McLachlan (1949) were cited four times between 1950 and 1951: Chemical Abstracts (1950); Water Pollution Abstracts (1951); Rudolphs, W. (1951) (Sewage and Industrial Wastes); and Love, S.K. (1951) (in a review of water analysis methods). Thus Lyne and McLachlan’s 1949 paper was widely noted in abstract or review literature by the scientific community in 1950-51, but mainly for its analytical method. The paper was then mentioned by Jettmar (1957) in an informative review of groundwater contamination which appeared in a German-language Austrian journal. Jettmar (1957) (but not Lyne and McLachlan) was cited again in an annotated bibliography on groundwater pollution (Summers & Spiegel, 1974). The only other significant citation to Lyne and McLachlan (1949), which partly recognised the importance of the groundwater context, was by Stanley and Eliassen (1961) in their “Status of Knowledge of Groundwater Contaminants” produced for the US Federal Housing Administration (FHA). A brief factual paragraph is found at the end of the section on “Pesticides – Experience to date”; inclusion within that section detracts from the recognition of TCE’s significance.

Lyne & McLachlan (1949) are additionally cited in:
  • Klein (1957) (and 1962 update), a book on pollution of rivers, which reports Lyne and McLachlan’s analytical method;
  • Schollmeyer (1960), a German-language paper which applies Lyne and McLachlan’s analytical method to biological samples;
  • Mancy & Weber (1971), who cite Lyne and McLachlan’s colorimetric analytical method for the analysis of chemical wastewater;
  • NAS (1975), where Lyne and McLachlan (1949) are cited as an example of how production-plant losses of chlorinated hydrocarbons to the environment may cause contamination of water wells. (In fact the cases quoted were solvent-user industries, rather than production plants).

There are two other indirect citations of Lyne and McLachlan’s work via Jettmar (1957), within the pesticide-based literature of USPHS (1964) and Cope (1966). These references are distorted and muddled third-hand accounts that categorise the work within the emerging pesticide literature and serve little to exemplify the influence of Lyne & McLachlan’s work, in fact rather the opposite.

Rivett (2008) concluded that none of the aforementioned documents, though citing the Lyne & McLachlan article, support a conclusion that Lyne & McLachlan triggered recognition of the problem of groundwater contamination by TCE or other solvents at a local, national or international level during the 1950s through to the 1970s. Certainly the citations indicate an awareness of Lyne & McLachlan’s work, however, this interest is largely peripheral with citing authors mostly concerned with the analysis method for other water/sample types, pesticide contamination and ocean pollution. There are only five citations (three direct, two indirect citing Jettmar) that present the groundwater pollution finding of Lyne & McLachlan at all. All are very factual, none develop significantly the implication of the article, and some are misrepresenting. Based on the published literature, the groundwater pollution aspect of Lyne & McLachlan’s 1949 paper was therefore insignificantly recognised over the crucial 1950-75 period.

Subsequent work by Lyne and McLachlan
A brief review of Lyne and McLachlans’ later careers failed to find evidence of subsequent work published by them on solvent-contaminated sites. Lyne continued to work with the Reading Borough Council within environmental health roles until his retirement. Although the remit of local authorities still included water-related health issues, much work may have likely focused on other topics such as air and food quality. Additionally, from around the 1950s groundwater management in the UK increasingly moved from local authority control to the regional water authorities or companies, and later the national regulator (Environment Agency, previously the National Rivers Authority). Lyne additionally headed the Lyne, Martin & Radford Public Analyst laboratory that analysed soil/water samples in the 1970–80s – according to reports from my own colleagues who were working at that time on solvent-contaminated sites. However, Lyne, Martin and Radford’s remit was to analyse the samples provided to them, with no direct site involvement or interpretation of site data.

Other publications by Lyne and McLachlan reflect their predominant public analyst/environmental health-based analysis work, which was wide-ranging. McLachlan has at least forty and Lyne at least seven publications in the scientific literature. Their publications include (citations are not listed here, but may be found in Rivett et al., 2006): “The analysis of starch sugar degradation products by selective fermentation” (McLachlan, 1928); “Drinking waters for cattle” (McLachlan, 1930); “The analysis of green teas” (McLachlan and Stern, 1934); “The treatment of waste waters in the food industry” (McLachlan, 1935); “Notes on the selective oxidation of vinegar” (Lyne and McLachlan, 1946); “Use of anthrone in the determination of trace amounts of glycerol” (Lyne et al., 1968); and by McLachlan, “A new approach to the analysis of fish cakes” (Burgess et al., 1970).

Publications in their later life are informative of their interests over that period when the solvents problem was generally emerging. These are foodstuff-related and include reviews of the starch analysis literature by Lyne (1976) and “Health foods – a Public Analyst’s view” by McLachlan (1972). McLachlan’s final publication (McLachlan, 1983) was published when he was 89 years old and is simply entitled “Old age”! Lyne’s final publication was in fact a short obituary of McLachlan (Lyne, 1992). He makes no reference to their joint work on TCE, rather, he notes McLachlan’s pioneering work on building decay relating to air pollution and microbiological action (McLachlan, 1940). No further publications by Lyne and McLachlan on TCE, chlorinated solvents, or groundwater have been found after their 1949 paper.

Recognition of the solvents-in-groundwater problem
Rivett et al. (2006) review in detail the recognition of the solvents-in-groundwater problem in the UK and internationally. There is no evidence that Lyne and McLachlan’s work and their continued presence in Reading generated any early appreciation of the solvents-in-groundwater problem, either locally in the Reading area or in the UK.  Review of UK groundwater-contamination literature has failed to uncover any UK authors citing Lyne and McLachlan (1949) until recently (Rivett et al., 2005). It is doubtful that any of the UK groundwater or geosciences practitioners would have subscribed to The Analyst, and it would appear that the UK water-related research community remained oblivious to the paper’s existence.

Some early references to potential TCE groundwater problems occurred in the late 1960s to early 1970s. For example, Section III, para. 32 of a toxic waste disposal report identified TCE as a threat to water quality (Ministry of Housing and Local Government, 1970). Waste Management Paper No. 9 (DoE, 1976), a guidance on the disposal of halogenated hydrocarbon solvents, also recognised the threat. Groundwater quality work in the 1960s-70s, however, focused on landfill, nitrate and sewage effluent pollution. Limited, proactive, investigation of chlorinated solvents in groundwater did occur under the DoE (Department of Environment) research programme into pollution from landfills (DoE, 1978), with analysis and detection of chlorinated solvents in the chalk unsaturated zone below the Ingham landfill site (Suffolk) in 1974. ICI appears to be the earliest industry to assess the impact of chlorinated solvents to the UK environment in the early-to-mid 1970s (Pearson and McConnell, 1975). ICI’s monitoring programme over 1972-73 was largely in the vicinity of its main Runcorn production facility. Pearson and McConnell (1975) reported chlorinated solvents at parts per billion or less in freshwaters, sea waters and marine sediments. They did not directly report their groundwater data, but indicate “Significantly we have never detected organochlorines in well waters”. This early work still failed to trigger solvent problem recognition. Yorkshire Water Authority workers Stanton and Firth (1978) tentatively identified PCE in some groundwater samples during trihalomethane (THM) surveys of water supplies. The often presumed earliest UK case of TCE/PCE detected in groundwater was in the limited groundwater supply surveys of Fielding et al. (1981). The first national groundwater survey (209 sites) was not conducted until 1984 and revealed significant TCE contamination (Folkard 1986).

The UK’s most notable groundwater-contamination legal case involved PCE contamination of the Cambridge Water Company Sawston borehole in 1983 (Misstear et al., 1998). Following discovery of the pollution in 1983 and subsequent investigations, the case was heard in the High Court in 1991, the Court of Appeal in 1992, and was finally decided by the House of Lords in 1993. Common Law principles applied. The Lords decided recovery of damages in nuisance depended on foreseeability, and the alleged polluter could not have reasonably foreseen the consequences of the solvent release at that time. The key question was the date at which a ‘solvent user’ was reasonably able to foresee the potential harm that solvents could cause in the aquatic environment. The Lords decided this was after 1976. This date was based upon concerns beginning to be expressed around that time on the presence in groundwater of low PCE and TCE concentrations as potential carcinogens, and the publicity this issue was receiving outside of scientific journals (NIOSH, 1975). The case appears to have been completely unaware of the existence of Lyne & McLachlan (1949). 

Internationally, after Lyne and McLachlan’s early work, it appears that Schwille, the pioneer of DNAPL solvents research (Schwille, 1988), should be credited with the earliest proactive investigation of groundwater contamination by solvents. Schwille in the late 1990s prepared an unpublished report describing the reasons for his early recognition of the solvents problem (personal communication, Cherry, J.A.). He details two TCE case studies in Germany, in 1967 and 1973, that were not made public. There is no mention of Lyne and McLachlan in Schwille’s reporting. Furthermore, none of the other European publications that reported early discoveries of solvent contamination of groundwater make any reference to Lyne & Mclachlan. These include Grob and Grob (1974) and Giger and Molnar-Kubica (1978) in Switzerland, who accidentally discovered PCE contamination of wells while testing the tap water in their own laboratory. Also included in this early work is (probably) the first European national survey, in The Netherlands, where analysis for halogenated VOCs (volatile organic compounds) was conducted in all of the nation’s 232 ground-water supplies during 1976-78 (Zoeteman et al., 1981). Trichloroethylene was the predominant VOC detected.

Recognition of the solvents problem in the US has been reviewed by Pankow et al., 1996; Jackson 2004, 2003; and Amter & Ross, 2001. Stanley and Eliassen (1961) cited Lyne and McLachlan, but this did not stimulate any general recognition of the contamination problem. Not until the mid-to-late 1970s was the problem properly recognised in the US. It has been argued that recognition of the solvents problem should have been foreseen much earlier, in the 1940-50s (the era of Lyne & McLachlan) (Amter and Ross, 2001; Travis, 1998). However, there are almost no publications before 1975 that confirm solvent concentrations in US groundwater. Exceptions to this are reports in a 1961 US Public Health Service symposium (Middleton &Walton 1961; Miller 1961). The former paper listed TCE as an organic chemical that had caused one or more cases of groundwater contamination in the US; the sites in question, though, have not been determined. Occasional early references (Banks and Lawrence, 1953) make general remarks to the potential for solvents to cause groundwater problems, but it cannot be determined whether such remarks referred to chlorinated solvents per se, or to other miscible solvents or petroleum distillates discussed elsewhere in the 1950-60s literature.

The discovery by Rook (1974) in The Netherlands of trihalomethanes (THMs) formed during the chlorination of water containing humic compounds (and more routine availability of improved gas chromatography (GC)) was pivotal.  This led to widespread testing for THM and other chlorinated solvents in US public water supplies, including some from groundwater. US EPA national surveys in 1974-76 (Symons et al., 1975; Brass et al., 1977) revealed the presence of chlorinated compounds and led to the conclusion between ca.1976-79 that many groundwaters were contaminated with chlorinated solvents (Pankow et al., 1996). Thus the widespread discovery of chlorinated solvents in groundwater was somewhat fortuitous and essentially derived from increased public health concerns over THMs. Concurrently, TCE and PCE were identified as potential carcinogens (NIOSH, 1975, 1978). Hundreds of solvent-contaminated sites were documented by 1980 in the US. Emergence of the solvent problem there thus preceded events in the UK, but likewise appears uninfluenced by Lyne & McLachlan’s early work.

Lyne and McLachlan’s analytical method
Lyne and McLachlan (1949) used a colorimetric analysis method to analyse dissolved amounts of TCE in water, based on a modification of the Fujiwara pyridine–sodium hydroxide reaction. Fujiwara (1914) had observed a crimson colour when traces of trichloromethane (TCM; chloroform; CHCl3) or trichloroacetic acid were added to a boiling mixture of pyridine and strong aqueous alkali. A review of the Fujiwara reaction by Seto and Schultze (1956) reports that other halogenated hydrocarbons may give a positive Fujiwara test under suitable conditions and that without proper modification the method is non-specific. They cite ten investigators from the 1930s-1950s who adapted the Fujiwara procedure. Lyne and McLachlan were not cited.

Lyne and McLachlan (1949) provide few details of their specific Fujiwara pyridine alkali reaction, but it appears to be the first application for analysing water samples. A number of citations do cite Lyne and McLachlan (1949), primarily for its analytical method (Love, 1951; Klein, 1957; Schollmeyer, 1960; Mancy & Weber, 1971). These publications concern media or environments other than groundwater. In contrast to many papers which adopted the Fujiwara method, Lyne and McLachlan (1949) did not utilise any instrumentation, which was being marketed in the 1940s, for measuring the colour reaction. Love (1951) notes that “increasing use of instruments in the analysis of water is apparent. Photometers and spectrophotometers of various kinds have largely displaced visual observations in colorimetric analysis.” The importance of spectrophotometers was later illustrated by Seto and Schultze (1956), who used the Fujiwara method on urine samples. Examination of their absorbance-concentration graph indicates a detection limit approaching ca. 1 μg/L. Camisa (1975) also used the Fujiwara method on water samples and indicated “acceptable sensitivity (1 μg)”, but again raises reliability and specificity issues. These findings indicate it was possible to quantify occurrence of Fujiwara-reactive chlorinated solvents (TCE, TCM) to around μg/L levels in the 1950s, although unequivocal identification of contaminants was not possible.

Application of the Fujiwara method to water analyses by other workers in the UK is not apparent. Montgomery and Conlon (1967) provide examples of GC analysis for the estimation of sludge chlorinated-solvent content (potentially adaptable to water samples). They did not cite the Fujiwara method, but suggested an aggressive Stepanow reduction as an alternative. Lovelock,  the inventor of the ECD (electron capture detector) widely used in GC analysis of chlorinated solvents (Lovelock, 1961), and an early pioneer of atmospheric chlorofluorocarbons research, was unaware of Lyne and McLachlan’s work (personal communication, Lovelock, J.E.). There was, however, UK interest in the Fujiwara test in other areas, notably the rapid detection of racehorse doping by the sedative chloral hydrate (Moss & Rylance, 1966; Badcock, 2000). There was potentially more use, albeit with reservations, of the reaction in the US. Schaumburg (1990) reports that prior to 1975 “the Fujiwara colorimetric method of TCE determination was commonly used”, although citations are unfortunately not provided. Camisa (1975) lists various shortcomings of the method, and Schaumburg (1990) notes the most important problem for water analysis was the inability of the Fujiwara method to distinguish TCE from other chlorinated solvents. Rivett et al. (2006) indicate that although Fujiwara-based analysis of water samples, particularly groundwater, failed to trigger a widespread recognition of the solvents problem, there still remains interest in the Fujiwara reaction for water analysis. Angel et al.’s (1987) work on Fujiwara reaction mechanisms (that had proved quite elusive) underpinned the development of a Fujiwara-based optrode [optical electrode] that automatically and specifically monitors TCM and TCE in water to concentrations below 1 μg/L (Burge & Hoffman, 2003). It remains the only colorimetric method available to monitor dissolved TCE at low concentrations.

Re-emergence of Lyne & McLachlan (1949)
Modern citations of Lyne & McLachlan (1949) include Colten & Skinner (1994, 1996), Colten (1998), Travis (1998, 2002a,b), Jackson (1999, 2003, 2004), Amter & Ross (2001, 2008), and Shifrin (2005). These authors are all located in North America with the exception of Travis, who is based in Israel. The earliest citations, from the mid 1990s, by Colten & Skinner, coincide with the passing of the last surviving author, Lyne, in 1996. Prior to this time, including the period in the 1970-80s when chlorinated solvent contamination of the environment was becoming more recognised, Lyne and McLachlan’s work was unknown to practitioners who worked on groundwater contamination. Appreciation in the UK of Lyne and McLachlan’s work occurred several years after the citations in the USA. A few UK-based workers were conversationally aware of the paper’s existence, and Rivett et al. (2005, 2006) were the first UK authors to recognise the significance of Lyne & McLachlan’s work in contaminated groundwater research – more than 55 years after the original publication.

Conclusions and relevance
Lyne and McLachlan (1949) is believed to be the world’s earliest known publication concerning TCE (or chlorinated solvent) occurrence in groundwater. It appears to be a “one-off” publication on groundwater by these two UK authors, who at the time were Public Analysts working for several local authorities. The significance of their work for the contamination of groundwater only began to be recognised in the mid-to-late 1990s, in North America at least. The principal conclusion to be drawn is that Lyne and McLachlan failed to trigger any general recognition of the solvents-in-groundwater problem across the scientific, industrial, or regulatory communities. This unfortunate conclusion appears to be true at all levels – local, national and international. Their paper’s message was never disseminated to, or acted upon by, a wider audience, and it is questionable whether the potential prescience of their early work was ever really apparent to Lyne and McLachlan themselves. The historic lack of contribution to foreseeability of the problem means that Lyne & McLachlan (1949) is expected to have a limited influence on present-day litigation that involves historic solvent pollution of groundwater.

References
Amter, S.; Ross, B. (2001). Was contamination of southern California groundwater by chlorinated solvents foreseen? Environmental Forensics, 2(3), 179-184.

Amter, S.; Ross, B. (2008). Discussion of ‘A quest to locate sites described in the world’s first publication on trichloroethene contamination of groundwater’ by M. O. Rivett & L. Clark, Quarterly Journal of Engineering Geology and Hydrogeology, 40, 241–249. Quarterly Journal of Engineering Geology and Hydrogeology, 41, 491-493.

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* The constituent societies of the Royal Society of Chemistry were:
· The Chemical Society (founded in 1841)
· The Society for Analytical Chemistry (founded in 1874)
· The Royal Institute of Chemistry (founded in 1877)
· The Faraday Society (founded in 1903).
The Society for Analytical Chemistry (formerly The Society of Public Analysts) was subsumed by the RSC’s Analytical Division. See also: Association of Public Analysts http://www.publicanalyst.com/index.html
 
MICHAEL RIVETT
University of Birmingham
Birmingham, B15 2TT UK
E-mail: M.O.RIVETT@bham.ac.uk
http://www.gees.bham.ac.uk/staff/rivettmo.shtml
 
Dr Michael Rivett is a Senior Lecturer in the Water Sciences Group at the School of Geography, Earth & Environmental Sciences, University of Birmingham. This article is based, in part, on Dr Rivett’s recent publications and on his presentation at the ECG’s 2009 symposium on Contaminated Land: Contaminant Transport and Fate. Dr Rivett welcomes any additional relevant information readers may have on Lyne and McLachlan’s work.
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