Analysis of polycyclic aromatic hydrocarbons (PAHs) and their derivatives in biochar treated stormwater.

Polycyclic aromatic hydrocarbons (PAHs), oxygenated PAHs (oxy-PAHs) and nitrogen heterocyclic polycyclic aromatic compounds (N-PACs) are persistent and semi-volatile organic compounds primarily formed due to incomplete combustion of organic material or, in the case of the derivatives, through transformation reactions of PAHs. Their presence in the environment is ubiquitous and many of them have been proven carcinogenic, teratogenic, and mutagenic. These toxic pollutants can therefore pose a threat to both ecosystem and human health and urges for remediation strategies for PAHs and derivatives from water bodies. Biochar is a carbon-rich material resulting from the pyrolysis of biomass resulting in a very porous matter with high surface area for an enhanced interaction with chemicals. This makes biochar a promising alternative for filtering micropollutants from contaminated aquatic bodies. In this work, a previously developed and validated methodology for the analysis of PAHs, oxy-PAHs and N-PACs in surface water samples was adapted for its utilization in biochar treated stormwater with special emphasis on scaling down the solid-phase extraction as well as including an additional filtering step for the removal of particulate matter in the media.•Optimized extraction method for PAHs, oxy-PAHs and N-PACs from stormwater treated with biochar.•Biochar strongly impacts the stormwater matrix and, therefore, additional steps are required in the extraction methodology.•Solid-phase extraction combined with GC-MS have been used to analyse PAHs, oxy-PAHs and N-PACs in stormwater treated with biochar.

Organic micropollutants, heavy metals and pathogens in anaerobic digestate based on food waste.

Anaerobic digestate based on food waste is increasingly used as fertilizer in food production. This study examined the characteristics of anaerobic digestate based on food waste from three biogas plants in Sweden. The characterization included measurements of heavy metals (n = 7), chemicals of emerging concern (CECs), such as currently used drugs and pesticides (n = 133), and an extended range of food-borne pathogens, including two notable sporeformers and some widespread antibiotic-resistant bacteria. The amounts of Escherichia coli, enterococci, and Salmonella and the concentrations of the target heavy metals were all below the maximum accepted levels at all three locations studied. However, the spore-forming Bacillus cereus was found to be present at high levels in samples from all three biogas plants. Among the 133 CECs investigated, 48 were detected at least once, and the highest concentrations were found for pyroxidine, nicotine, caffeine, theobromine, and nicotine. The biofertilizers from the different biogas plants had similar CEC profiles, which indicate similarities in household waste composition and thorough mixing in the biogas plants. If this profile is found to be spatially and temporally consistent, it can help regulators to establish priority lists of CECs of top concern. Assuming increasing use of biofertilizers for food production in the future, it would be beneficial to have concentration limits for CECs Risk estimation based on risk quotients (RQs) indicated generally low environmental risks associated with application of biofertilizer to soils for food crop production. However, the toxicity of CEC mixtures needs to be considered when estimating the risks from application of biofertilizers on agricultural land or in other production systems.

Spatial distribution of legacy pesticides in river sediment from the Republic of Moldova.

Historical use of organochlorine pesticides (OCPs) in the Republic of Moldova could pose a potential risk for the aquatic environment due to the persistence, bioaccumulation and toxic properties of these environmental pollutants. However, knowledge on environmental concentrations of legacy OCPs in Moldova is limited. In this study, surface sediment from the two main rivers; Dniester (8 sites, n = 15) and Prut (6 sites, n = 12), and two tributary rivers; Bîc (11 sites, n = 11) and Raut (6 sites, n = 6), were collected during 2017-2018 and analyzed for hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs) and their transformation products (DDDs and DDEs) using gas chromatography coupled to mass spectrometry (GC-MS/MS). Sediment concentrations of Æ©6DDX (1.9-140 ng g-1 dry weight (dw)) and Æ©4HCHs (n.d-2.5 ng g-1 dw) were found. In the big rivers, the average Æ©6DDX concentration (18 ng g-1 dw) were 35 times higher than Æ©4HCHs (0.51 ng g-1 dw). Whereas, in the small rivers the average Æ©6DDX concentration (32 ng g-1 dw) was approximately 41 times higher than Æ©4HCHs (0.77 ng g-1 dw). Compared to previous studies from Eastern Europe, the sediment levels were generally similar as found in Moldova's neighboring countries (Romania and Ukraine). Overall, the contamination profile indicates long-term ageing of OCPs used in the past in the agricultural sector. Less than half of the sites (45%) had levels that pose a potential risk for benthic organisms. Hence, further work is needed to determine the bioaccumulation of OCPs in the aquatic food web in this region and the associated risks to ecosystems and human health.

Unraveling the chemodiversity of halogenated disinfection by-products formed during drinking water treatment using target and non-target screening tools.

To date, there is no analytical approach available that allows the full identification and characterization of highly complex disinfection by-product (DBP) mixtures. This study aimed at investigating the chemodiversity of drinking water halogenated DBPs using diverse analytical tools: measurement of adsorbable organic halogen (AOX) and mass spectrometry (MS)-based target and non-target analytical workflows. Water was sampled before and after chemical disinfection (chlorine or chloramine) at four drinking water treatment plants in Sweden. The target analysis had the highest sensitivity, although it could only partially explain the AOX formed in the disinfected waters. Non-target Fourier transform ion cyclotron resonance (FT-ICR) MS analysis indicated that only up to 19 Cl and/or Br-CHO formulae were common to all disinfected waters. Unexpectedly, a high diversity of halogenated DBPs (presumed halogenated polyphenolic and highly unsaturated compounds) was found in chloraminated surface water, comparable to that found in chlorinated surface water. Overall, up to 86 DBPs (including isobaric species) were tentatively identified using liquid chromatography (LC)-Orbitrap MS. Although further work is needed to confirm their identity and assess their relevance in terms of toxicity, they can be used to design suspect lists to improve the characterization of disinfected water halogenated mixtures.

Effect-based assessment of recipient waters impacted by on-site, small scale, and large scale waste water treatment facilities - combining passive sampling with in vitro bioassays and chemical analysis.

Waste water treatment facilities are a major sources of organic micropollutants (MPs) in surface water. In this study, surface water samples were collected from seven sites along a river system in Uppsala, Sweden, during four seasons and evaluated based on the occurrence of MPs in the samples and bioactivity using in vitro bioassays. The sampling sites were differentially impacted by on-site sewage treatment facilities (OSSFs), small scale, and large scale waste water treatment plants (WWTPs). The bioassays used included activation of aryl hydrocarbon receptor (AhR), estrogen receptor (ER), nuclear factor kappa-light-chain-enhancer of activated B cells (NFkB), nuclear factor erythroid 2-related factor 2 (Nrf2), and androgen receptor (AR). Occurrence of 80 MPs, were analyzed using liquid chromatography coupled to tandem mass spectrometry. Most water samples induced AhR activity, and all sampling sites showed a similar profile regarding this activity. With the exception of one water sample, we did not detect any NFkB, Nrf2 or AR activity of the water samples. The exception was a sample impacted by OSSFs, which showed an activity in multiple bioassays, but the activity could not be explained by the occurrence of target MPs. The occurrence of MPs showed a spatial trend, with the highest number and amount of MPs detected in the samples collected downstream of the WWTPs, where up to 47 MPs were detected in one single sample. A seasonal variation was observed with highest levels of MPs and highest AhR activities in samples collected in June and September 2015. However, neither the seasonal activity nor the on-site activity could be explained by the measured MPs, suggesting unknown contributory agents in the water.

Impact of on-site, small and large scale wastewater treatment facilities on levels and fate of pharmaceuticals, personal care products, artificial sweeteners, pesticides, and perfluoroalkyl substances in recipient waters.

One of the main risks associated with effluents from both wastewater treatment plants (WWTPs) and on-site sewage treatment facilities (OSSFs) is the release of micropollutants (MPs) in receiving water bodies. However, the impact of MPs present in the effluents of OSSFs in the aquatic environment has not been studied so far. The current study evaluates the impact of the effluents of OSSFs and small-to-large scale WWTPs on natural waters. The discharge of 74 MPs was assessed including pharmaceuticals, personal care products, pesticides, artificial sweeteners and perfluoroalkyl substances (PFASs). The sampling was carried out within a Swedish catchment and included three sites that are exclusively affected by OSSFs and other sites that are mainly affected by WWTPs or a mixture of sources (7 sites, 28 samples). Results show that although OSSFs serve a much smaller total number of people, the MPs emitted from OSSFs reached the aquatic environment in significant quantities (concentrations of >150ngL-1 of ∑MPs). The composition profiles for sites affected by WWTPs were similar and were dominated by sucralose (27% of the ∑MPs), caffeine (27% of the ∑MPs), lamotrigine (10% of the ∑MPs), desvenlafaxine (5% of the ∑MPs), and diclofenac (4% of the ∑MPs). In contrast, the sites affected by OSSFs showed high variability, exhibiting a different profile from those affected by WWTPs and also from each other, demonstrating that OSSFs are not homogeneous sources of MPs. Some specific compounds, such as diethyltoluamide (DEET) and caffeine, were proportionally much more important at sites affected by OSSFs than at sites affected by WWTPs (representing a much higher percentage of the ∑MPs in the OSSFs). In contrast, PFASs did not show high concentration variation among the different sampling sites and the composition profiles were relatively similar, indicating that these substances follow different routes of entry into the aquatic environment.

Development and comparison of gas chromatography-mass spectrometry techniques for analysis of flame retardants.

The restrictions on the use of legacy flame retardants (FRs) have increased the need of alternative FRs to comply with fire safety legislations. In this study, the feasibility of three different gas chromatography-mass spectrometry (GC-MS) techniques were investigated for the analysis of 102 legacy and alternative FRs including polybrominated diphenyl ethers (PBDEs, n=27), halogenated FRs (HFRs, containing bromine and/or chlorine, n=46), and organophosphorous FRs (OPFRs, n=29). The tested techniques included GC-single MS with (i) electon impact (EI) ionization and (ii) negative chemical ionization (NCI), and (iii) GC-tandem MS (MS/MS) with EI ionization. Out of the tested FRs, 90 could be detected under the used conditions on at least one of the three instrument setups. Later experiments included a selection of these FRs. For the majority of tested PBDEs (5 out of 6) and HFRs (24 out of 26), EI-MS/MS provided the highest detectability (i.e. the lowest detection limits), while for most tested OPFRs (8 out of 13), EI-MS performed better. The influence of matrix components on the analysis of FRs (n=45) was investigated by analyzing a fortified surface water sample with the technique with the lowest selectivity, EI-MS. Both peak enhancement and suppression were observed, and significant correlations between matrix effects and several physico-chemical properties (e.g., retention time and boiling point) were found for PBDEs. In a separate clean-up experiment using natural water spiked with legacy and alternative FRs (n=30), alumina provided the highest mean recovery (90%) in comparison to acidified silica (67%) and Florisil (78%). This study provides new knowledge on analysis of FRs including a wide range of alternative FRs, and it will aid in the efforts of FR monitoring in the environment.

Atmospheric pathways of chlorinated pesticides and natural bromoanisoles in the northern Baltic Sea and its catchment.

Long-range atmospheric transport is a major pathway for delivering persistent organic pollutants to the oceans. Atmospheric deposition and volatilization of chlorinated pesticides and algae-produced bromoanisoles (BAs) were estimated for Bothnian Bay, northern Baltic Sea, based on air and water concentrations measured in 2011-2012. Pesticide fluxes were estimated using monthly air and water temperatures and assuming 4 months ice cover when no exchange occurs. Fluxes were predicted to increase by about 50 % under a 2069-2099 prediction scenario of higher temperatures and no ice. Total atmospheric loadings to Bothnian Bay and its catchment were derived from air-sea gas exchange and "bulk" (precipitation + dry particle) deposition, resulting in net gains of 53 and 46 kg year(-1) for endosulfans and hexachlorocyclohexanes, respectively, and net loss of 10 kg year(-1) for chlordanes. Volatilization of BAs releases bromine to the atmosphere and may limit their residence time in Bothnian Bay. This initial study provides baseline information for future investigations of climate change on biogeochemical cycles in the northern Baltic Sea and its catchment.

Trace analysis of polychlorinated dibenzo-p-dioxins, dibenzofurans and WHO polychlorinated biphenyls in food using comprehensive two-dimensional gas chromatography with electron-capture detection.

Trace analysis of 2,3,7,8-polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and the 12 WHO-PCBs (four non-ortho and eight mono-ortho congeners that have been assigned toxic equivalence factors, TEFs, by the World Health Organisation) was conducted by comprehensive two-dimensional gas chromatography with a micro electron-capture detector (GC x GC-microECD). Four food matrices (fish oil from herring, spiked cows' milk, vegetable oil and an eel extract) were analysed by two GC x GC laboratories, and four GC-HRMS laboratories generated reference values. The two GC x GC laboratories used different column combinations for separating the target analytes. For the first dimension, non-polar DB-XLB and VF-1 columns were used, and for the second dimension, an LC-50 liquid crystalline column with unique selectivity for planar compounds. The congener-specific and total toxic equivalence (TEQ) data obtained using DB-XLB x LC-50 were in good agreement with results obtained by the GC-HRMS laboratories. The WHO-PCB data obtained with the VF-1 x LC-50 combination was also good, but the PCDD/F concentrations were sometimes overestimated due to matrix interferences. GC x GC-microECD using DB-XLB x LC-50 seems to fulfil the European Community requirements of a screening method for PCDD/F and WHO-PCB TEQ in food.

Air-sea gas exchange of HCHs and PCBs and enantiomers of alpha-HCH in the Kattegat Sea region.

Concentrations and air-water gas exchange of polychlorinated biphenyls (PCBs) and hexachlorocyclohexanes (HCHs) were determined in nine paired air and water samples. The samples were collected monthly in the Kattegat Sea between December 1998 and November 1999. Average fugacity and flux values indicated that PCBs were oversaturated in the water, while HCHs were net deposited. Variations were large over the year, especially during spring and summer. Air parcel back trajectories suggested that air concentrations over the Kattegat Sea are largely dependent of air mass origin. Seasonal trends were detected for airborne HCHs and for PCBs in water. The air and water enantiomeric compositions of alpha-HCH indicated that a larger portion of alpha-HCH in air originated from the underlying water during summer than during winter.

Chiral pesticides in soil and water and exchange with the atmosphere.

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.