Organic Chemical Contaminants in Water System Infrastructure Following Wildfire.

Wildfires have destroyed multiple residential communities in California in recent years. After fires in 2017 and 2018, high concentrations of benzene and other volatile organic compounds (VOCs) were found in public drinking water systems in fire-affected areas. The sources of the contamination and appropriate remediation have been urgent matters for investigation. This study characterizes target and non-target VOCs and semi volatile organic compounds (SVOCs) in water from a highly contaminated service line after the 2018 Camp Fire (Paradise, CA). Ninety-five organic compounds were identified or tentatively identified in the service line. Laboratory combustion experiments with drinking water pipes made of polyvinyl chloride (PVC), cross-linked polyethylene (PEX) and high-density polyethylene (HDPE) and a review of the literature were used to evaluate potential sources of the detected chemicals. Among the service line contaminants were thirty-two compounds associated with PVC pyrolysis and twenty-eight organic compounds also associated with the pyrolysis of polyethylene. The service line sample also contained fifty-five compounds associated with uncontrolled burning of biomass and waste materials. The findings support hypotheses that wildfires can contaminate drinking water systems both by thermal damage to plastic pipes and intrusion of smoke. Residual chlorine disinfectant in the water system modifies the contaminant distribution observed.

Lowering detection limits for 1,2,3-trichloropropane in water using solid phase extraction coupled to purge and trap sample introduction in an isotope dilution GC-MS method.

Purge and trap sample introduction (PTI) has been the premier sampling and preconcentration technique for gas chromatographic determination of volatile organic compounds (VOCs) in drinking water for almost 50 years. PTI affords sub parts-per-billion (ppb) detection limits for purgeable VOCs including fixed gases and higher boiling hydrocarbons and halocarbons. In this study the coupling of solid phase extraction (SPE) to PTI was investigated as a means to substantially increase enrichment and lower detection limits for the emerging contaminant, 1,2,3-trichloropropane (TCP). Water samples (500 mL) were dechlorinated, preserved with a biocide, and spiked with the isotope labeled internal standard, d5-TCP. The entire 500 mL sample was extracted with activated carbon or carbon molecular sieve SPE cartridges, and then eluted with dichloromethane -- excess solvent was removed in a nitrogen evaporator and diethylene glycol "keeper" remaining was dispersed in 5 mL of water for PTI GC-MS analysis. The experimental Method Detection Limit (MDL) for TCP was 0.11 ng/L (ppt) and accuracy was 95-103% in sub-ppt determinations. Groundwater samples including impaired California sources and treated water (n = 21) were analyzed with results ranging from below the method reporting limit (0.30 ng/L) to > 250 ng/L. Coupling of SPE with PTI may provide similar reductions in detection limits for other VOCs with appropriate physical-chemical properties.

Identification of volatile and semivolatile compounds in chemical ionization GC-MS using a mass-to-structure (MTS) Search Engine with integral isotope pattern ranking.

The mass-to-structure or MTS Search Engine is an Access 2010 database containing theoretical molecular mass information for 19,438 compounds assembled from common sources such as the Merck Index, pesticide and pharmaceutical compilations, and chemical catalogues. This database, which contains no experimental mass spectral data, was developed as an aid to identification of compounds in atmospheric pressure ionization (API)-LC-MS. This paper describes a powerful upgrade to this database, a fully integrated utility for filtering or ranking candidates based on isotope ratios and patterns. The new MTS Search Engine is applied here to the identification of volatile and semivolatile compounds including pesticides, nitrosoamines and other pollutants. Methane and isobutane chemical ionization (CI) GC-MS spectra were obtained from unit mass resolution mass spectrometers to determine MH(+) masses and isotope ratios. Isotopes were measured accurately with errors of <4% and <6%, respectively, for A + 1 and A + 2 peaks. Deconvolution of interfering isotope clusters (e.g., M(+) and [M - H](+)) was required for accurate determination of the A + 1 isotope in halogenated compounds. Integrating the isotope data greatly improved the speed and accuracy of the database identifications. The database accurately identified unknowns from isobutane CI spectra in 100% of cases where as many as 40 candidates satisfied the mass tolerance. The paper describes the development and basic operation of the new MTS Search Engine and details performance testing with over 50 model compounds.

Electrolyte-induced ionization suppression and microcystin toxins: ammonium formate suppresses sodium replacement ions and enhances protiated and ammoniated ions for improved specificity in quantitative LC-MS-MS.

This study examines the effects of electrolytes on microcystin (MC) electrospray ionization (ESI) mass spectrometry and quantitative LC-MS-MS. Sodium replacement ions (SRI) are prominent in MC ESI spectra in protic solvents such as HPLC grade methanol. In a methanol-water-0.006% acetic acid (v/v) gradient, envelopes with up to 11 SRI were apparent in both the +1 and +2 charge states with structures [M + Na(x) - (x-1)H](+) and [M + Na(x) - (x-2)H](+2). The m/z 135 product ion, [Ø-CH(2)-CH=O-CH(3)](+), widely used in tandem LC-MS-MS determination of MC, is a low collision energy fragment of many doubly charged MC precursor ions (e.g., [M+Na+H](+2), [M+Na+NH(4)](+2), M+Na+H+CH(3)OH](+2), [M+2H](+2)). These phenomena impair congener-specific LC-MS-MS detection of MC and degrade quantitative accuracy and precision. Pulse addition experiments established that ammonium formate (AF) strongly suppresses SRI in both +1 and +2 charge states and enhances MH(+) and MNH(4)(+) adducts in neutral MC. Addition of the buffer either post-column or by incorporation in the mobile phase increases specificity for all of the MC which were determined as the MNH(4)(+) > MH(+) and MH(+) > [MH - 134](+) transitions for neutral MC (MCLA, MCLF, MCLW) and [M+2H](+2) > 135(+) and [M+2H](+2) > [M+2H - 135](+) transitions for arginine-containing MC (MCLR, MCYR, MCRR). These findings shed light on mechanisms of electrolyte-induced ionization suppression, and demonstrate beneficial use of a buffer electrolyte for improved specificity and analytical ruggedness in quantitative LC-MS-MS.

Identification of unknowns in atmospheric pressure ionization mass spectrometry using a mass to structure search engine.

This study evaluates a new model for identifying unknown compounds in atmospheric pressure ionization mass spectrometry based on a mass-to-structure (MTS) paradigm. In this method, rudimentary ESI spectrum interpretation is required to recognize key spectral features such as MH (+), MNa (+), and MNH 4 (+), which lead to the unknown's monoisotopic mass. The unknown's mass is associated directly with known organic compounds using an Access 2003 database containing records of 19,438 substances assembled from common sources such as the Merck Index, pesticide and pharmaceutical compilations, and chemical catalogues. A user-defined mass tolerance (+/-0.001-0.5 Da) is set according to the instrument mass accuracyunit mass resolution data require a wide mass tolerance ( approximately 0.5 Da) while tolerances for accurate mass data can be as narrow as +/-0.001 Da. Candidate structures retrieved with the MTS Search Engine appear in a report window providing formulas, mass error, and Internet links. This paper provides examples of structure elucidation with 15 organic compounds based on ESI mass spectra from both unit mass resolution (e.g., quadrupole ion trap and triple-stage quadrupole) and accurate mass instruments (e.g., TOF and Q-TOF). Orthogonal information (e.g., isotope ratios and fragmentation data) is complementary and useful for ranking candidates and confirming assignments. The MTS Search Engine identifies unknowns quickly and efficiently, and supplements existing interpretation schemes for unknown identification.

Direct determination of dialkyl phosphates by strong anion-exchange liquid chromatography/atmospheric pressure chemical ionization mass spectrometry using a quadrupole ion trap instrument.

The direct determination of dialkyl phosphates (DAPs) in water by strong anion-exchange (SAX) liquid chromatography/atmospheric pressure chemical ionization (APCI) mass spectrometry was investigated. The SAX high-performance liquid chromatography (HPLC) column was eluted with methanol/water gradients containing ammonium formate (AF) separating the DAPs which included six dimethyl- and diethyl-substituted phosphates, thiophosphates, and dithiophosphates. The high buffer concentrations required for separation were compatible with -ve APCI, but in +ve APCI the DAPs were unstable giving anomalous ions such as [M+15]+ and [M+29]+. These ions are believed to result from ion molecule reactions with CH3OH2+ in the plasma. DAPs are very stable in -ve APCI being detected as abundant [M-H](-) ions, even with 200 mM AF. At higher AF concentration formate clusters ([M+45](-) and [M+91](-)) were seen. Fragmentation by collision-activated dissociation (CAD) was more efficient for deprotonated ethyl-substituted DAPs which lost ethylene followed by ethanol. APCI instrument detection limits were in the low ng/mL range and the response was highly linear. Isotope dilution quantitation using d10-diethyl dithiophosphate (DEDTP) as an internal standard produced an instrument detection limit of 2 ng DEDTP/mL and method detection limit (MDL) of 9.3 ng/mL with accuracy of 99% (spike concentration, 25 ng/mL). DAP mixtures required storage in cold, dry conditions and alcohol solvents should be avoided because of solvolysis reactions.

Near UV quantum yields for rotenone and piperonyl butoxide.

Rotenone and piperonyl butoxide (PBO) mixtures, so-called "synergized" rotenone, are invaluable in fisheries management where they are used to protect the habitat of endangered, native species and promote desirable gamefish populations. Continued use of synergized rotenone is threatened by inadequate control of persistence in surface water, especially where drinking water supplies are impacted. The photochemical kinetics of these chemicals were studied in the laboratory with a goal to better understand their fate in natural water. Disappearance quantum yields (phi) were determined in polychromatic light from fluorescent lamps emitting maximally at 350 nm. Rotenone, PBO and trifluralin, an actinometer, were irradiated as aqueous solutions at 25 or 50 microg L(-1) and the piscicides were determined by electrospray-liquid chromatography-mass spectrometry (ESI-LC-MS). In the photoreactor rotenone and PBO photodegraded with first-order half-lives of 500 and 220 min, respectively, and corresponding quantum yields of 0.00015 and 0.034. Rotenone absorbs sunlight strongly, while PRO does not. Differences in spectal overlap tended to counteract the disparities in phi and, in general, mathematical modeling indicates moderately rapid direct photolysis rates for both substances in surface water.

Atmospheric pressure ionization LC-MS-MS determination of urushiol congeners.

This paper describes atmospheric pressure ionization (API) LC-MS-MS determination of urushiols, 3-n-alkenyl- and -alkyl-substituted catechols responsible for poison oak dermatitis. Urushiol was isolated from Western poison oak according to the method of Elsohly et al. (1) (J. Nat. Prod. 1982, 45, 532-538)-the purified preparation contained C(17)- and C(15)-substituted urushiols with zero, one, two, and three double bonds as determined from GC-MS analysis of trimethylsilyl derivatives. Urushiol mixtures were separated on a C(18) reversed phase HPLC column with a methanol-water gradient with urushiols eluting in 100% methanol. Atmospheric pressure chemical ionization (APCI) produced primarily [M - H](-) and MH(+) molecule ions. Electrospray ionization (ESI) yielded [M - H](-) and adduct ions including [M + Cl](-). Daughter ions of [M - H](-) included quinoid radical anions ([M - H - H(2)](-) and m/z 122(-)) and a benzofuran phenate (m/z 135(-)). A suite of hydrocarbon fragments were produced by collision-induced dissociation of MH(+) directly or via an intermediate [MH - H(2)O](+) daughter ion. Six urushiol congeners, one not previously reported in poison oak, were determined by negative ion API-LC-MS-MS with detection limits of approximately 8 pg/microL (ESI) and approximately 800 pg/microL (APCI). API-LC-MS-MS was used to determine urushiol in surface wipes, air samples, and plant materials.