A case study of organic micropollutants in a major Swedish water source - Removal efficiency in seven drinking water treatment plants and influence of operational age of granulated active carbon filters.
Department of Aquatic Sciences and Assessment, Swedish University of Agricultural Sciences SLU, Box 7050, SE-750 07 Uppsala, Sweden. Electronic address: rikard.troger@slu.se.
A wide range of organic micropollutants (n?=?163) representing several compound categories (pharmaceuticals, pesticides, per- and polyfluorinated alkyl substances, flame retardants, phthalates, food additives, drugs and benzos) were analysed in water samples from the Göta Älv river (Sweden's second largest source water). The sampling also included raw water and finished drinking water from seven drinking water treatment plants and in addition a more detailed sampling at one of the treatment plants after six granulated active carbon filters of varying operational ages. In total, 27 organic micropollutants were detected, with individual concentrations ranging from sub?ng?L-1 levels to 54?ng?L-1. The impact of human activities along the flow path was reflected by increased concentrations downstream the river, with total concentrations ranging from 65?ng?L-1 at the start of the river to 120?ng?L-1 at the last sampling point. The removal efficiency was significantly (p?=?0.014; one-sided t-test) higher in treatment plants that employed granulated active carbon filters (n?=?4; average 60%) or artificial infiltration (n?=?1; 65%) compared with those that used a more conventional treatment strategy (n?=?2; 38%). The removal was also strongly affected by the operational age of the carbon filters. A filter with an operational age of 12?months with recent addition of ~10% new material showed an average removal efficiency of 92%, while a 25-month old filter had an average of 76%, and an even lower 34% was observed for a 71-month old filter. The breakthrough in the carbon filters occurred in the order of dissolved organic carbon, per- and polyfluorinated alkyl substances and then other organic micropollutants. The addition of fresh granulated active carbon seemed to improve the removal of hydrophobic organic compounds, particularly dissolved organic carbon and per- and polyfluorinated alkyl substances.
The enantiomers of chiral pesticides are often metabolised at different rates in soil and water, leading to nonracemic residues. This paper reviews enantioselective metabolism of organochlorine pesticides (OCPs) in soil and water, and the use of enantiomers to follow transport and fate processes. Residues of chiral OCPs and their metabolites are frequently nonracemic in soil, although exceptions occur in which the OCPs are racemic. In soils where enantioselective degradation and/or metabolite formation has taken place, some OCPs usually show the same degradation preference--e.g., depletion of (+)trans-chlordane (TC) and (-)cis-chlordane (CC), and enrichment of the metabolite (+)heptachlor exo-epoxide (HEPX). The selectivity is ambivalent for other chemicals; preferential loss of either (+) or (-)o,p-DDT and enrichment of either (+) or (-)oxychlordane (OXY) occurs in different soils. Nonracemic OCPs are found in air samples collected above soil which contains nonracemic residues. The enantiomer profiles of chlordanes in ambient air suggests that most chlordane in northern Alabama air comes from racemic sources (e.g., termiticide emissions), whereas a mixture of racemic and nonracemic (volatilisation from soil) sources supplies chlordane to air in the Great Lakes region. Chlordanes and HEPX are also nonracemic in arctic air, probably the result of soil emissions from lower latitudes. The (+) enantiomer of alpha-hexachlorocyclohexane (alpha-HCH) is preferentially metabolised in the Arctic Ocean, arctic lakes and watersheds, the North American Great Lakes, and the Baltic Sea. In some marine regions (the Bering and Chukchi Seas, parts of the North Sea) the preference is reversed and (-)alpha-HCH is depleted. Volatilisation from seas and large lakes can be traced by the appearance of nonracemic alpha-HCH in the air boundary layer above the water. Estimates of microbial degradation rates for alpha-HCH in the eastern Arctic Ocean and an arctic lake have been made from the enantiomer fractions (EFs) and mass balance in the water column. Apparent pseudo first-order rate constants in the eastern Arctic Ocean are 0.12 year(-1) for (+)alpha-HCH, 0.030 year(-1) for (-)alpha-HCH, and 0.037 year(-1) for achiral gamma-HCH. These rate constants are 3-10 times greater than those for basic hydrolysis in seawater. Microbial breakdown may compete with advective outflow for long-term removal of HCHs from the Arctic Ocean. Rate constants estimated for the arctic lake are about 3-8 times greater than those in the ocean.
BACKGROUND, AIM, AND SCOPE: The main pathway for human exposure to the highly toxic polychlorinated-p-dioxins and polychlorinated furans [polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)] is via dietary intake. Other exposure pathways may, however, be important in close proximity to point sources, such as wood preservation sites, where PCDD/F contaminated chlorophenols (CP) were previously used. In this study, a heavily PCDD/F contaminated CP saw mill site in Sweden was investigated. Human exposure through a broad spectrum of exposure pathways was assessed. Such studies are in demand since the question whether contaminated sites represent a current or future risk can only be answered by detailed site-specific risk assessments. MATERIALS AND METHODS: Sampling of exposure media (soil, air, groundwater, raspberries, carrots, potatoes, grass, milk, eggs, and chicken fodder) was made. Exposure media concentrations and congener distribution patterns were used to investigate the mobilization of PCDD/Fs from soil to the environment and to calculate exposure levels for adults. Blood serum levels from site-exposed and control individuals were also analyzed. RESULTS: Congener distribution patterns at the site were generally dominated by a specific marker congener (1234678-HpCDF), which is highly abundant in the polluted soil. The dioxin toxic equivalents (TEQ) concentrations were notably elevated as compared to national reference samples for most exposure media, and the marker congener was a major contributor to increased TEQ levels. There were also indications of soil-to-air volatilization of tetra- and penta-CDD/Fs. People who participated in the restoration of a contaminated building showed higher levels of 1234678-HpCDF compared to controls, and calculated exposure levels suggest that several site-specific exposure routes may be of importance for the daily intake of PCDD/F. CONCLUSIONS, RECOMMENDATIONS, AND PERSPECTIVES: Despite low mobility of higher chlorinated PCDD/Fs, these contaminants were transferred from the polluted soil to the surroundings and into human tissue. The extent of increased exposure from contaminated sites depends on the PCDD/F source strength of the soil, composition of the pollution, human activities, and dietary patterns of the residents. Impact from the contaminated soil on other exposure media was seen also for areas with low to moderate soil contamination. In the future, not only the levels of PCDD/F soil pollution but also the composition must be considered in risk assessments of contaminated sites.
Per- and polyfluoroalkyl substances (PFAS) were measured systematically in a snowpack in northern Sweden to determine chemical behaviour during seasonal melt. Average PFAS concentrations were generally low, but displayed a wide range with median (range) concentrations of PFOA and PFOS of 66.5 pg L(-1) (ND-122) and 20.5 pg L(-1) (2.60-253) respectively. Average concentrations of the shorter chain, C4 and C5 perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs), were ~10-fold higher. Differences in the PFAS concentrations and profile were observed between surface snow and deeper layers, with evidence of PFAS migration to deeper snow layers as melt progressed. Chemical loads (ng m(-2)) for C4-9 PFCAs decreased gradually as melt progressed, but increased for C4, C6-8 PFSAs and the longer chain C10-12 PFCAs. This enrichment in the diminishing snowpack is an unusual phenomenon that will affect PFAS elution with meltwater and subsequent entry to catchment surface waters.
This study is the first attempt to quantify environmental fluxes per capita of organic contaminants discharged from on-site sewage treatment facilities (OSSFs) in affected recipients. Five sites were monitored around the River Fyris in Sweden: three mainly affected by OSSFs and two mainly affected by municipal sewage treatment plants (STPs). Gas chromatography-mass spectrometry was used to determine environmental concentrations of 30 anthropogenic contaminants, including organophosphorus compounds, rubber and plastic additives, UV stabilizers, fragrances, surfactant ingredients and polycyclic aromatic hydrocarbons. Uni- and multivariate statistical analysis of the most frequently detected contaminants showed that median fluxes per capita of tris(1,3-dichloro-2-propyl) phosphate, tris(1-chloro-2-propyl) phosphate, tris(2-chloroethyl) phosphate, and n-butylbenzene sulfonamide were similar at OSSF and STP sites, but the mass fluxes per capita of tris-(2-butoxyethyl) phosphate, 2-(methylthio)benzothiazole, and galaxolide, were significantly lower (~2-3-fold) at OSSF sites than at STP sites (Mann-Whitney, a?=?0.05). Differences between these sites were larger in samples collected in summer and autumn than in samples collected in winter. Deviations likely originated from differences in fate processes and distances between source and sampling sites. Further studies are needed to characterize mass fluxes per capita of contaminants in waters that directly receive discharges from OSSFs.
Department of Aquatic Sciences and Assessment, Swedish University of Agricultural Sciences (SLU), Box 7050, SE-75007 Uppsala, Sweden. Electronic address: rikard.troger@slu.se.
A multi-residue screening method for simultaneous measurement of a wide range of micropollutants in drinking water (DW) resources was developed. The method was applied in a field study in central Sweden on water from source to tap, including samples of surface water (upstream and downstream of a wastewater treatment plant, WWTP), intake water before and after a DW treatment plant (DWTP, pilot and full-scale), treated DW leaving the plant and tap water at end users. Low detection limits (low ng?L-1 levels) were achieved by using large sample volumes (5 L) combined with ultra performance liquid chromatography high resolution mass spectrometry (UPLC-HRMS). In total, 134 different micropollutants were analyzed, including pesticides, pharmaceuticals and personal care products (PPCPs), drug-related compounds, food additives, and perfluoroalkyl substances (PFASs). Of these 134 micropollutants, 41 were detected in at least one sample, with individual concentrations ranging from sub ng?L-1 levels to ~80?ng?L-1. Two solid phase extraction (SPE) cartridges (Oasis HLB and Bond-Elut ENV) were shown to be complementary in the field study, with three compounds detected exclusively using HLB. The total concentration in treated drinking water (56-57?ng?L-1) was at a similar level as upstream from the WWTP (79-90?ng?L-1). The composition of micropollutants changed along the water path, to a higher fraction of food additives and PFASs. Median treatment efficiency in the full-scale DWTP was close to 0%, but with high variability for individual compounds. In contrast, median treatment efficiency in the pilot-scale DWTP was ~90% when using nanofiltration followed by a freshly installed granulated active carbon (GAC) filter.
Non-target screening and prioritization of potentially persistent, bioaccumulating and toxic domestic wastewater contaminants and their removal in on-site and large-scale sewage treatment plants.
On-site sewage treatment facilities (OSSFs), which are used to reduce nutrient emissions in rural areas, were screened for anthropogenic compounds with two-dimensional gas chromatography-mass spectrometry (GC×GC-MS). The detected compounds were prioritized based on their persistence, bioaccumulation, ecotoxicity, removal efficiency, and concentrations. This comprehensive prioritization strategy, which was used for the first time on OSSF samples, ranked galaxolide, a-tocopheryl acetate, octocrylene, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, several chlorinated organophosphorus flame retardants and linear alkyl benzenes as the most relevant compounds being emitted from OSSFs. Twenty-six target analytes were then selected for further removal efficiency analysis, including compounds from the priority list along with substances from the same chemical classes, and a few reference compounds. We found significantly better removal of two polar contaminants 2,4,7,9-tetramethyl-5-decyn-4,7-diol (p=0.0003) and tris(2-butoxyethyl) phosphate (p=0.005) in soil beds, a common type of OSSF in Sweden, compared with conventional sewage treatment plants. We also report median removal efficiencies in OSSFs for compounds not studied in this context before, viz. a-tocopheryl acetate (96%), benzophenone (83%), 2-(methylthio)benzothiazole (64%), 2,4,7,9-tetramethyl-5-decyn-4,7-diol (33%), and a range of organophosphorus flame retardants (19% to 98%). The environmental load of the top prioritized compounds in soil bed effluents were in the thousands of nanogram per liter range, viz. 2,4,7,9-tetramethyl-5-decyn-4,7-diol (3000ngL-1), galaxolide (1400ngL-1), octocrylene (1200ngL-1), and a-tocopheryl acetate (660ngL-1).
Soil with high levels of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) is found at contaminated sites all over the world. Transfer of PCDD/Fs from contaminated soil to the food chain could lead to elevated human exposure. As a complement to available monitoring data, multimedia fate and exposure modeling can be applied to support risk assessment of sites with PCDD/F contaminated soil. In this study, we evaluated the performance of the CalTOX fate and exposure model for 2,3,7,8-substituted PCDD/Fs against measured concentrations in air, soil, grass, carrots, potatoes, milk, meat, and eggs from a contaminated site in northern Sweden. The calculated total toxic equivalent (TEQ) concentrations agree with measurements within a factor of 10 for all exposure media but one. Results for individual congeners demonstrated that the model did not always perform well at describing key processes that mobilize PCDD/Fs out of soils, such as transfer into root crops and ingestion of soil by chickens. Uncertainty in only a small subset of input parameters affects the model output. Improved information and models describing transfer of soil particles onto leafy vegetation by rain splash and biotransfer factors for PCDD/Fs to milk, meat, and eggs are particular research needs to reduce uncertainties in model-based assessments.
Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and metals in scots pine (Pinus sylvestris) needles from Eastern and Northern Europe: Spatiotemporal patterns, and potential sources.
Pine needles were sampled to determine levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and metals in Scots pine (Pinus sylvestris) needles at industrial, urban and background sites in Sweden (SW), Czech Republic (CZ) and Slovakia (SK). Spatial and temporal patterns of PCDD/Fs in pine needles were investigated and principal component analysis (PCA) used to determine spatial patterns, potential sources and transport of PCDD/Fs. Levels of PCDD/Fs in pine needles were generally greatest near to industrial sites (?2,3,7,8-PCDD/Fs (lower bound (LB)): 6 ng kg(-1) - 190 ng kg(-1)) compared to urban and background sites (?2,3,7,8-PCDD/Fs (LB): 0.90 ng kg(-1) - 20 ng kg(-1)). Using metal contamination in pine needles helped to detect spatial patterns and separate local thermal sources of PCDD/Fs.
Department of Aquatic Sciences and Assessment, Swedish University of Agricultural Sciences (SLU), Box 7050, 75007 Uppsala, Sweden. Electronic address: jakob.gustavsson@oru.se.
Boreal forests store large amounts of atmospherically deposited (semi-)persistent organic pollutants (POPs). The terrestrial POPs may be exported to streams and rivers through processes that are heavily impacted by seasonality. In this screening study, concentrations of 4 legacy and 45 alternative flame retardants (FRs) were determined in the dissolved and particulate phase in streams within a relatively pristine boreal catchment in northern Europe (Krycklan Catchment Study; 3 sites) and in rivers more impacted by human activities further downstream towards the Baltic Sea (3 sites). The sampling included the main hydrological seasons (snow-free, snow-covered, and spring flood) and was conducted during two consecutive years (2014-2016). Of the 49 analyzed FRs, 11 alternative halogenated FRs (HFRs), 13 alternative organophosphorus FRs (OPFRs), and 4 legacy polybrominated diphenyl ethers (PBDEs) were detected in at least one sample. The average bulk (dissolved + particulate) concentrations of ?FRs (including all sites) were highest for ?HFRs (38?±?70?ng?L-1), followed by the ?OPFRs (3.9?±?4.9?ng?L-1) and the ?PBDEs (0.0040?±?0.016?ng?L-1). Bulk concentrations of HFRs, OPFRs, and PBDEs were highly variable with season and sampling location, e.g., during spring flood, bulk concentrations were up to 600 times, 3.7 times, and 4.9 times higher for HFRs, OPFRs and PBDEs, respectively, than during periods of lower flow. Bulk concentrations of ?OPFRs, were elevated at all sites ~6?days before the actual start of the spring flood in 2015, suggesting that hydrophobicity fractionation had occurred within the snowpack. Similar to previous studies of other POPs in the same headwater catchment, there was a general trend that levels of ?FRs were higher at the mire site than at the forested site. Annual fluxes of FRs were found to be ~15 times higher downstream the city of Umeå compared to at the outlet of the pristine catchment. This study should be regarded as a screening study considering the large number of diverse FRs analyzed and variability in the results.
