Occurrence, distribution, spatio-temporal variability and source identification of n-alkanes and polycyclic aromatic hydrocarbons in water and sediment from Loskop dam, South Africa.

In this study, the spatial and temporal variations in the levels of C8-C40 n-alkanes and 18 polycyclic aromatic hydrocarbons (PAHs) in water and sediment from Loskop Dam (Mpumalanga Province South Africa), were investigated between 2015 and 2017. In addition, their sources, which have not been well defined, were also studied over the period. This water body is sourced from a historically contaminated water body, the Olifants River, which flows through areas where a range of industrial and agricultural activities take place. Mass crocodile and fish mortalities have been recorded in this aquatic system, and contamination by organic pollutants were highlighted as a contributing factor. The total average n-alkane concentrations in water and sediments ranged from 0.574±00811 to 18.8±1.39 µg/L and 4760±243 to 30700±906 µg/kg, respectively. Similarly, PAHs were detected at total average concentrations of between 0.150±00494 and 49.8±6.86 µg/L in water and 61.6±5.95 to 2618±300 µg/kg. n-Alkane and PAH diagnostic ratios indicated a mixture of sources of these compounds, attributed to terrestrial, submerged and floating plant material, as well as petrogenic and pyrogenic combustion. Inlet, middle and upper segment site clustering was observed with non-metric multidimensional scaling (NMDS) and hierarchical cluster analysis (HCA), mainly driven by the prevalence of PAHs at the inlet sites and n-alkanes in the upper reaches. By using indicator compounds, the sources of contamination could be predicted. The strategy described here can be applied to any water body for continuous long-term monitoring of pollutant levels and to identify sources attributing to water pollution.

Quantification, source apportionment and risk assessment of polycyclic aromatic hydrocarbons in sediments from Mokolo and Blood Rivers in Limpopo Province, South Africa.

The presence of polycyclic aromatic hydrocarbons (PAHs) in the environment is of major concern since some of these compounds are highly persistent, toxic (causing cancer) and wide spread pollutants. The objective of this study was to evaluate the levels of PAHs in sediment samples collected from Blood and Mokolo Rivers in Limpopo Province, South Africa. The PAHs in sediments were extracted using optimized microwave-assisted extraction (MAE) method. The quantification of sixteen (16) PAHs in sediments was done by gas chromatography-flame ionization detector (GC-FID). The levels of PAHs recorded in sediment samples from Blood River ranged between 0.015 and 3.25 mg kg-1. The concentrations of PAHs obtained in sediments from Mokolo River (0.047 to 52.7 mg kg-1) were higher than those recorded in sediments from Blood River. The PAHs ratios indicated that both pyrogenic and petrogenic could be the sources of these compounds in both rivers. Toxic equivalency factors (TEFs) and benzo(a)pyrene equivalent (BaPE) were used to estimate the potential human health risk of PAHs in quantitative terms. The assessment of ecotoxicological risk indicated that the sediment samples collected from Mokolo River are at high toxicity risk while sediments from Blood River are at low sediment toxicity risk.

Speciation of major and trace elements leached from coal fly ash and the kinetics involved.

The combustion of coal in thermal power plants may result in high concentrations of elements in the coal fly ash remaining that may be toxic to living organisms or pose a risk to the environment. This study was aimed at determining the concentrations of potentially toxic elements in coal fly ash leachates, in an attempt to simulate natural processes that influence the environment. Powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and elemental composition studies were employed to characterize the physicochemical properties of the parent coal fly ash. The effect of various leaching parameters, including the pH of leaching solutions, the volume ratio of leaching solutions to the mass of coal fly ash, leaching time and temperature, were investigated. Moreover, the kinetics of the leaching of toxic elements from coal fly ash was also investigated by considering that the leaching process is governed by dissolution. Zero order, pseudo-first order, pseudo-second order, power function, simple Elovich and parabolic diffusion kinetic models were used to evaluate the leaching process. The experimental results indicate that the pH and leaching time had the most significant effect on the leaching behavior of elements from coal fly ash.

Characterization of Nine Isomers in Commercial Samples of Perfluoroethylcyclohexanesulfonate and of Some Minor Components Including PFOS Isomers.

Electrochemical fluorination of 4-ethylbenzenesulfonyl halides produces a mixture of compounds that has found extensive use as an erosion inhibitor in aircraft hydraulic fluids. This paper reports a study of the composition of commercial samples of this material from two industrial scale manufacturers in terms of the structures and relative concentrations of their components, the major of which is perfluoroethylcyclohexanesulfonate (PFECHS). Fractionation of one of these mixtures by column chromatography produced fractions in which all significant components were of sufficient purity to allow assignment of their structures by 19F NMR spectroscopy. Assessment of the relevant signals in the 19F NMR spectra of the commercial mixtures by integration revealed the presence of 14 constituents at levels ≥0.5% in terms of molar contributions. Ten of these involve five pairs of geometric isomers, including cis- and trans-PFECHS which accounted for between 55% and 60% of the components present. Three constituents were determined to be isomers of perfluorooctanesulfonate (PFOS), two branched and the other linear PFOS itself. The availability of samples of the various components also allowed us to identify the compounds responsible for the peaks observed when the commercial samples were analyzed by LC/MS using either C18 or perfluorophenyl stationary phases.

Levels of potentially toxic metals in water, sediment and peat from Wonderfonteinspruit, North West Province, South Africa.

Environmental monitoring of the levels of potentially toxic metals is of importance because of possible adverse effects on living species. This study was conducted to assess the levels of Cd, Cr, Cu, Hg, Mn, Pb, U and V in water, sediment and peat samples collected from the region of Wonderfonteinspruit. Water samples were simply filtered and acidified with HNO3 prior to analysis. Sediment and peat were oven-dried, ground, sieved and mineralised using a microwave digestion system. Concentrations of the selected elements in all samples were determined by inductively coupled plasma-mass spectrometry. A Zeeman mercury analyser was also used for quantification of Hg in the same sediment and peat samples. The method validation was carried out using SRM 1643e water and BCR 320R sediment certified reference materials. The results showed no significant difference at 95% level of confidence between the certified and measured values after using the Student's t-test. The levels of Cd, Cr, Cu, Pb, V and U found in rivers and dams were lower than the tentative South African water quality range guideline for domestic and irrigation purposes. However, water from dams and certain rivers was unsuitable for irrigation and domestic use.

Dechlorinated Analogues of Dechlorane Plus.

Degradation products of the chlorinated additive flame retardant Dechlorane Plus (DP) have been discovered globally. However, the identity of many of these species remains unknown due to a lack of available analytical standards, hindering the ability to quantitatively measure the amounts of these compounds in the environment. In the present study, synthetic routes to possible dechlorinated DP derivatives were investigated in an effort to identify the environmentally significant degradation products. The methano-bridge chlorines of anti- and syn-DP were selectively replaced by hydrogen atoms to give six new hydrodechlorinated DP analogues. The identity and absolute configuration of all of these compounds were confirmed by GC-MS, NMR spectroscopy, and X-ray diffraction studies. These compounds were observed in sediment samples from streams and rivers in relatively rural areas of Ontario and are thus environmentally relevant.

Single-step isolation of embelin using high-performance countercurrent chromatography and determination of the fatty acid composition of seeds of Embelia schimperi.

Embelin (2,5-dihydroxy-3-undecyl-p-benzoquinone) is known for its potent anthelmintic activity, but also for wound-healing, antidiabetic, anticonvulsant, antitumour, anti-inflammatory, analgesic, hepatoprotective, antioxidant, antibacterial and antispermatogenic activities. A high-performance countercurrent chromatography method was developed for the purification of embelin from an extract of the seeds of Embelia schimperi fruit. The optimized solvent system (n-hexane-ethylacetate-ethanol-water, 7:3:7:3) resulted in the isolation of 13.9 mg of embelin, directly from 100 mg of crude extract, in a single step within a short time (40 min). Although the compound appeared to be completely pure when analysed by ultra-performance liquid chromatography (UPLC) with photo diode array detection, the purity was established as ~90% by UPLC-mass spectrometry. Furthermore, we report the fatty acid composition of the seeds of E. schimperi fruit. Nine fatty acids were quantified from the fruit seed extract by gas chromatography-mass spectrometry, with linoleic (46.4%), palmitic (21.5%) and oleic (19.6%) acids making up the largest proportions.

Coupling of supercritical fluid chromatography to mass spectrometry for the analysis of Dechlorane Plus: Examination of relevant negative ion atmospheric pressure chemical ionization mechanisms.

During an investigation of the potential associated with coupling packed column supercritical fluid chromatography (pSFC) to mass spectrometry for the analysis of Dechlorane Plus and related compounds, it was found that negative ion atmospheric pressure chemical ionization (APCI) was a promising ionization technique. In the course of maximizing the responses associated with the target analytes, it proved useful to examine some aspects of the complex nature and reactivity of the corona discharge plasma generated to explain the observed ionization products. Various dopants/reagents were screened for both APCI and atmospheric pressure photoionization (APPI) in negative ion mode and mechanisms of ionization involving superoxide were elucidated based on the results obtained. Superoxide formation was found to be temperature dependent and directly related to the intensity of the ion cluster [M-Cl+O]- obtained for the target DP analytes. Furthermore, triethylamine was identified as a reagent capable of suppressing unwanted side reactions during the ionization process and maximizing response associated with the analytes of interest. The applicability of pSFC-APCI/MS for the separation and detection of Dechlorane Plus and related compounds was demonstrated by analyzing Lake Ontario sediment and comparing the results with values reported in the scientific literature.

Examination of technical mixtures of halogen-free phosphorus based flame retardants using multiple analytical techniques.

The application of phosphorus based flame retardants as replacements for commonly used halogenated flame retardants has been gaining interest due to the possibility that these compounds may have a less significant impact on human and environmental health. Unfortunately, little is known about the chemical compositions of many of the technical products (which often are mixtures) and a single separation technique for concurrent analysis of these types of compounds has not been identified. This paper reports the results of an investigation into the constituents of three halogen free organophosphate flame retardants (OPFRs), resorcinol bis(diphenyl phosphate) (RDBPP), bisphenol A bis(diphenyl phosphate) (BPA-BDPP), and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The major components of commercial samples of RDBPP and BPA-BDPP were isolated by preparative TLC and characterized by NMR. A commercial sample of DOPO was found to be essentially pure, but its analysis is complicated by the fact that it can exist in ring-open and ring-closed forms. With the structures of the components confirmed by NMR, multiple analytical separation techniques (gas chromatography (GC), liquid chromatography (LC), and packed column supercritical fluid chromatography (pSFC)) were investigated for the analysis of these three technical products. Packed column supercritical fluid chromatography allows the separation of the components of all three OPFRs, including the two forms of DOPO, in a single run.

Discovery of 40 Classes of Per- and Polyfluoroalkyl Substances in Historical Aqueous Film-Forming Foams (AFFFs) and AFFF-Impacted Groundwater.

Aqueous film-forming foams (AFFFs), containing per- and polyfluoroalkyl substances (PFASs), are released into the environment during response to fire-related emergencies. Repeated historical applications of AFFF at military sites were a result of fire-fighter training exercises and equipment testing. Recent data on AFFF-impacted groundwater indicates that ∼25% of the PFASs remain unidentified. In an attempt to close the mass balance, a systematic evaluation of 3M and fluorotelomer-based AFFFs, commercial products, and AFFF-impacted groundwaters from 15 U.S. military bases was conducted to identify the remaining PFASs. Liquid chromatography quadrupole time-of-flight mass spectrometry was used for compound discovery. Nontarget analysis utilized Kendrick mass defect plots and a "nontarget" R script. Suspect screening compared masses with those of previously reported PFASs. Forty classes of novel anionic, zwitterionic, and cationic PFASs were discovered, and an additional 17 previously reported classes were observed for the first time in AFFF and/or AFFF-impacted groundwater. All 57 classes received an acronym and IUPAC-like name derived from collective author knowledge. Thirty-four of the 40 newly identified PFAS classes derive from electrochemical fluorination (ECF) processes, most of which have the same base structure. Of the newly discovered PFASs found only in AFFF-impacted groundwater, 11 of the 13 classes are ECF-derived, and the remaining two classes are fluorotelomer-derived, which suggests that both ECF- and fluorotelomer-based PFASs are persistent in the environment.

Enantioselective Analytical- and Preparative-Scale Separation of Hexabromocyclododecane Stereoisomers Using Packed Column Supercritical Fluid Chromatography.

Hexabromocyclododecane (HBCDD) is an additive brominated flame retardant which has been listed in Annex A of the Stockholm Convention for elimination of production and use. It has been reported to persist in the environment and has the potential for enantiomer-specific degradation, accumulation, or both, making enantioselective analyses increasingly important. The six main stereoisomers of technical HBCDD (i.e., the (+) and (-) enantiomers of α-, ß-, and γ-HBCDD) were separated and isolated for the first time using enantioselective packed column supercritical fluid chromatography (pSFC) separation methods on a preparative scale. Characterization was completed using published chiral liquid chromatography (LC) methods and elution profiles, as well as X-ray crystallography, and the isolated fractions were definitively identified. Additionally, the resolution of the enantiomers, along with two minor components of the technical product (δ- and ε-HBCDD), was investigated on an analytical scale using both LC and pSFC separation techniques, and changes in elution order were highlighted. Baseline separation of all HBCDD enantiomers was achieved by pSFC on an analytical scale using a cellulose-based column. The described method emphasizes the potential associated with pSFC as a green method of isolating and analyzing environmental contaminants of concern.

Evidence for Anaerobic Dechlorination of Dechlorane Plus in Sewage Sludge.

The environmental occurrence of dechlorination moieties from the high production volume flame retardant, Dechlorane Plus (DP), has largely been documented; however, the sources have yet to be well understood. In addition, few laboratory-based studies exist which identify the cause for the occurrence of these chemicals in the environment or humans. Anaerobic dechlorination of the two DP isomers was investigated using a laboratory-simulated wastewater treatment plant (WWTP) environment where anaerobic digestion is used as part of the treatment regime. Known amounts of each isomer were added separately to sewage sludge which provided the electron-donating substrate and at prescribed time points in the incubation, a portion of the media was removed and analyzed for DP and any dechlorination metabolites. After 7 days, monohydrodechlorinated products were observed for both the syn- and anti-DP which were continued throughout the duration of our study (49 days) in an increasing manner giving a calculated formation rate of 0.48 ± 0.09 and 0.79 ± 0.12 pmols/day for syn- and anti-DP, respectively. Furthermore, we observed a second monohydrodechlorinated product only in the anti-DP isomer incubation medium. This strongly suggests that anti-DP is more susceptible to anaerobic degradation than the syn isomer. We also provide compelling evidence to the location of chlorine loss in the dechlorination DP analogues. Finally, the dechlorination DP moieties formed in our study matched the retention times and identification of those observed in surficial sediment located downstream of the WWTP.

Characterization and Biological Potency of Mono- to Tetra-Halogenated Carbazoles.

This paper deals with the characterization and aryl hydrocarbon receptor (AhR) agonist activities of a series of chlorinated, brominated, and mixed bromo/chlorocarbazoles, some of which have been identified in various environmental samples. Attention is directed here to the possibility that halogenated carbazoles may currently be emitted into the environment as a result of the production of carbazole-containing polymers present in a wide variety of electronic devices. We have found that any carbazole that is not substituted in the 1,3,6,8 positions may be lost during cleanup of environmental extracts if a multilayer column is utilized, as is common practice for polychlorinated dibenzo-p-dioxin (dioxin) and related compounds. In the present study, (1)H NMR spectral shift data for 11 relevant halogenated carbazoles are reported, along with their gas chromatographic separation and analysis by mass spectrometry. These characterization data allow for confident structural assignments and the derivation of possible correlations between structure and toxicity based on the halogenation patterns of the isomers investigated. Some halogenated carbazoles exhibit characteristics of persistent organic pollutants and their potential dioxin-like activity was further investigated. The structure-dependent induction of CYP1A1 and CYP1B1 gene expression in Ah-responsive MDA-MB-468 breast cancer cells by these carbazoles was similar to that observed for other dioxin-like compounds, and the magnitude of the fold induction responses for the most active halogenated carbazoles was similar to that observed for 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). 2,3,6,7-Tetrachlorocarbazole was one of the most active halogenated carbazoles and, like TCDD, contains 4 lateral substituents; however, the estimated relative effect potency for this compound (compared to TCDD) was 0.0001 and 0.0032, based on induction of CYP1A1 and CYP1B1 mRNA, respectively.

Distribution of polycyclic aromatic hydrocarbons in sediments of Akaki River, Lake Awassa, and Lake Ziway, Ethiopia.

The quantification of 14 polycyclic aromatic hydrocarbons (PAHs) was carried out in sediment samples collected from Akaki River, Lake Awassa, and Lake Ziway, Ethiopia. The concentration of PAHs in the samples was determined using gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode, after microwave-assisted extraction (MAE), using acetone/n-hexane (1:1, v/v) mixture. The accuracy of the method was determined by extracting and analyzing New York/New Jersey waterway sediment standard reference material (SRM 1944). The measured concentrations of PAHs in SRM 1944 agreed well with the certified values. In samples from Akaki River, Lake Awassa, and Lake Ziway, the total content of PAHs determined ranged from 0 to 3070 ng/g (average 534 ng/g), 24.9 to 413 ng/g (average 169 ng/g), and 15.0 to 305 ng/g (average 175 ng/g), respectively. Source ratios indicated that the PAHs were mainly from petrogenic origin. Sediments from all sampling sites indicated negligible levels of toxicity with no risk of adverse biological effects.

Binding of RDX to Cell Wall Components of Pinus sylvestris and Picea glauca and Three-Year Mineralisation Study of Tissue-Associated RDX Residues.

Contamination of soils with the explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX, Research Department Explosive) as a result of military applications is a large-area problem globally. Since coniferous trees dominate the vegetation of large areas of military land in Central Europe, particularly in Germany, the long-term fate of (14)C-RDX in the conifers Scots pine and Dwarf Alberta spruce was studied. Acetic acid was the most effective solvent for the removal of extractable RDX residues from homogenates of RDX-laden tree material (85%, 80-90% and 64-80% for roots, wood and needles, respectively). On average, only a fifth of RDX-derived (14)C was bound in non-extractable residues (NER). Within the main cell wall compartments, lignin was the dominant binding site for NER (needles: 32-62%; roots: 38-42%). Hemicellulose (needles: 11-18%; roots: 6-11%) and cellulose (needles: 12-24%; roots: 1-2%) were less involved in binding and a considerable proportion of NER (needles: 15-24%; roots: 59-51%) was indigestible. After three-year incubation in rot chambers, mineralisation of tree-associated (14)C-RDX to (14)CO2 clearly dominated the mass balance in both tree species with 48-83%. 13-33% of (14)C-RDX-derived radioactivity remained in an unleachable form and the remobilisation by water leaching was negligible (< 2%).

Halogenated indigo dyes: a likely source of 1,3,6,8-tetrabromocarbazole and some other halogenated carbazoles in the environment.

In recent years, a number of halogenated carbazoles have been detected in environmental samples. These emerging contaminants have been shown to be persistent and possess dioxin-like toxicological potential. The goal of this research was to examine the literature to determine likely anthropogenic origin(s) of halogenated carbazoles in the environment. The scientific literature indicated a number of pathways by which 1,3,6,8-tetrabromocarbazole could form in the manufacture of 5,5',7,7'-tetrabromoindigo. The U.S. production history of 5,5',7,7'-tetrabromoindigo correlates well with the concentration rise, decline, and disappearance of 1,3,6,8-tetrabromocarbazole in dated Lake Michigan sediments. Additionally, other halogenated carbazoles that have been found in environmental sediments can be explained by the production of other halogenated indigo dyes. 1,8-dibromo-3,6-dichlorocarbazole can be accounted for by the manufacture of 7,7'-dibromo-5,5'-dichloroindigo, while 1,3,6,8-tetrachlorocarbazole was found at relatively high concentration near the outfall of a U.S. manufacturer of 5,5',7,7'-tetrachloroindigo. Carbazoles containing an iodo-substituent can be explained by the use of iodine as a catalyst in the manufacture of halogenated indigo dyes. 3,6-Dichlorocarbazole measured in soils and dibromocarbazoles measured in more recently deposited sediments are not easily rationalized on the basis of an indigo related source and may be related to other anthropogenic sources or natural origins.

Occurrence, distribution, and ecological risk assessment of potentially toxic elements in surface sediments of Lake Awassa and Lake Ziway, Ethiopia.

Microwave-assisted acid digestion and modified aqua regia (HNO3:HCl:HF:H3BO3) leaching techniques were used for the determination of 15 potentially toxic elements (V, Cr, Fe, Mn, Co, Ni, Cu, Zn, As, Se, Ag, Cd, Sn, Hg and Pb) in sediment samples from Lake Awassa and Lake Ziway, Ethiopia. The digests were subsequently analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-optical emission spectrometry (ICP-OES). Mercury was directly determined in the solid samples using an elemental mercury analyzer. The precision and accuracy of the digestion procedures were verified using certified reference materials. The experimental results were in good agreement with the certified values (P < 0.05) and the recoveries were quantitative (>90%). The average relative standard deviations were below 10%. There is significant correlation between the two lakes at the 0.01 level (2-tailed). Using the sediment quality guidelines, both lakes are heavily polluted with Zn and some of the sites are heavily polluted with Cu, Ni and Pb. Based on effect range low (ERL) - effect range medium (ERM), in both lakes for Ag were greater than the ERM, indicating that the areas could be toxic to aquatic organisms, while for Cr, Cu, As and Hg the values were less than ERL.

Identification and occurrence of analogues of dechlorane 604 in Lake Ontario sediment and their accumulation in fish.

The dechlorane family of flame retardants, which includes Mirex (also known as Dechlorane), Dechlorane Plus (DP), and Dechloranes (Dec) 602, 603, and 604, were manufactured at a facility along the Niagara River, upstream of Lake Ontario. Some of these compounds remain in use. In a previous study, we found Mirex and Dec602 to have greater bioaccumulation potentials than Dec604 and DP based on calculated biota-sediment accumulation factors (BSAFs). In this study, analogues of Dec604, containing fewer bromines and mixed substitutions of bromine and chlorine, were identified in Lake Ontario sediment and fish using high and ultrahigh resolution mass spectrometric techniques. The tribromo-Dec604 (Br3Dec604) analogue, known as Dechlorane 604 Component B (Dec604 CB), was present in lake trout and whitefish at concentrations of 10-60 ng/g lipid weight, approximately 50-200 times greater than concentrations measured for Dec604. In addition, BrDec604 and Br2Dec604 analogues, and mixed Br2Cl2Dec604, Br3ClDec604, Br2ClDec604, and BrCl2Dec604 analogues were also present. We have shown that solutions of Dec604 and Dec604 CB exposed to UV-light undergo photodebromination and give rise to the analogues found in sediment and fish. Dec604 CB and other lesser halogenated analogues of Dec604 show greater bioaccumulation potentials than Dec604, Dec602 and DP, based on BSAFs, which highlight the need to consider likely impurities and degradation products in the assessment of persistent, bioaccumulative, and toxic compounds.

Identification of potential novel bioaccumulative and persistent chemicals in sediments from Ontario (Canada) using scripting approaches with GC×GC-TOF MS analysis.

This work describes a single and fast approach using a filtering script as a means of prioritizing sample processing of data acquired by GC×GC-TOF MS for the identification of potentially novel persistent and bioaccumulative halogenated chemicals. The proposed script is based on the recognition of a generic halogenated isotope cluster pattern that allows for the simultaneous detection of chlorinated, brominated, or mixed halogen-substituted compounds in a single classification. Once developed, the script was applied to the identification of organohalogens in stream sediments collected across the southern region of Ontario (Canada). Classified peaks were first compared with available analytical standards and reference libraries to confirm the known chemicals. Unknown potential persistent organic pollutants (POPs) were evaluated for occurrence within the samples and high resolution mass spectrometry was used in order to identify some of the most prevalent compounds in the samples and resulting in the identification of three decachlorinated dechlorane analogs (C18H14Cl10), two undecachlorinated dechlorane species (C18H13Cl11), and a novel mixed chloro/bromo-carbazole (C12H5NCl2Br2) in a number of sediments analyzed. Relative peak abundances of these unknown halogenated compounds were in the same order of magnitude or slightly higher than levels observed for conventional POPs detected in the samples.