Seasonal variations in air concentrations of 27 organochlorine pesticides (OCPs) and 25 current-use pesticides (CUPs) across three agricultural areas of South Africa

For decades pesticides have been used in agriculture, however, the occurrence of legacy organochlorine pesticides (OCPs) and current-use pesticides (CUPs) is poorly understood in Africa. This study investigates air concentrations of OCPs and CUPs in three South African agricultural areas, their spatial/seasonal variations and mixture profiles. Between 2017 and 2018, 54 polyurethane foam-disks passive air-samplers (PUF-PAS) were positioned in three agricultural areas of the Western Cape, producing mainly apples, table grapes and wheat. Within areas, 25 CUPs were measured at two sites (farm and village), and 27 OCPs at one site (farm). Kruskal-Wallis tests investigated area differences in OCPs concentrations, and linear mixed-effect models studied differences in CUPs concentrations between areas, sites and sampling rounds. In total, 20 OCPs and 16 CUPs were detected. A median of 16 OCPs and 10 CUPs were detected per sample, making a total of 11 OCPs and 24 CUPs combinations. Eight OCPs (trans-chlordane, o,p'-/p,p'-dichlorodiphenyldichloroethylene (DDE)/dichlorodiphenyltrichloroethane (DDT), endosulfan sulfate, γ-hexachlorocyclohexane and mirex) and two CUPs (carbaryl and chlorpyrifos) were quantified in all samples. p,p'-DDE (median 0.14 ng/m(3)) and chlorpyrifos (median 0.70 ng/m(3)) showed the highest concentrations throughout the study. Several OCPs and CUPs showed different concentrations between areas and seasons, although CUPs concentrations did not differ between sites. OCPs ratios suggest ongoing chlordane use in the region, while DDT and endosulfan contamination result from past-use. Our study revealed spatial and seasonal variations of different OCPs and CUPs combinations detected in air. Further studies are needed to investigate the potential cumulative or synergistic risks of the detected pesticides

Widespread pesticide distribution in the European atmosphere questions their degradability in air

Risk assessment of pesticide impacts on remote ecosystems makes use of model-estimated degradation in air. Recent studies suggest these degradation rates to be overestimated, questioning current pesticide regulation. Here, we investigated the concentrations of 76 pesticides in Europe at 29 rural, coastal, mountain, and polar sites during the agricultural application season. Overall, 58 pesticides were observed in the European atmosphere. Low spatial variation of 7 pesticides suggests continental-scale atmospheric dispersal. Based on concentrations in free tropospheric air and at Arctic sites, 22 pesticides were identified to be prone to long-range atmospheric transport, which included 15 substances approved for agricultural use in Europe and 7 banned ones. Comparison between concentrations at remote sites and those found at pesticide source areas suggests long atmospheric lifetimes of atrazine, cyprodinil, spiroxamine, tebuconazole, terbuthylazine, and thiacloprid. In general, our findings suggest that atmospheric transport and persistence of pesticides have been underestimated and that their risk assessment needs to be improved

Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and chlorinated pesticides in background air in central Europe - investigating parameters affecting wet scavenging of polycyclic aromatic hydrocarbons

Concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and chlorinated pesticides (CPs) were measured in air and precipitation at a background site in central Europe. Sigma PAH concentrations in air and rainwater ranged from 0.7 to 327.9 ng m(-3) and below limit of quantification (< LOQ) to 2.1 x 10(3) ng L-1. The concentrations of PCBs and CPs in rainwater were < LOQ. Sigma PCB and Sigma CP concentrations in air ranged from < LOQ to 44.6 and < LOQ to 351.7 pg m(-3), respectively. The potential relationships between PAH wet scavenging and particulate matter and rainwater properties were investigated. The concentrations of ionic species in particulate matter and rainwater were significantly correlated, highlighting the importance of particle scavenging process. Overall, higher scavenging efficiencies were found for relatively less volatile PAHs, underlining the effect of analyte gas-particle partitioning on scavenging process. The particulate matter removal by rain, and consequently PAH wet scavenging, was more effective when the concentrations of ionic species were high. In addition, the elemental and organic carbon contents of the particulate matter were found to influence the PAH scavenging

Long-range atmospheric transport of PAHs, PCBs and PBDEs to the central and eastern Mediterranean and changes of PCB and PBDE congener patterns in summer 2010

The central and eastern Mediterranean is a receptor area for persistent organic pollutants (POPs) emitted in western, central and eastern Europe, particularly during summer. Atmospheric concentrations of PCBs, DDXs, PBDEs, penta- and hexachlorobenzene were measured during a ship-borne survey in the summer of 2010. The concentration of PCBs (sum of 7 congeners) was 3.61 (2.08-7.72) pg m(-3), of which 6.7% was associated with the particulate phase. The mean concentration of DDT isoi-ners and their metabolites, DDE and DDD, was 2.60 (0.46-7.60) pg m(-3) (particulate mass fraction theta = 0.097), of penta- and hexachlorobenzene 0.22 (<039-2.80) pg m(-3) and 6.29 (2.48-24.16) pg m(-3), respectively, and of PBDEs (sum of 8 congeners) 7.31 (2.80-19.89) pg m(-3). The air masses studied had been transported mostly across central Europe, some crossing western Europe. The observed changes of PCB congener patterns along transport routes are in agreement with the perception that the reaction with the OH radical is dominating PCB atmospheric lifetime, and indicate an overestimation of the second order gas-phase reaction rate coefficient of PCB:153 with OH by structure-activity relationship. (C) 2015 Elsevier Ltd. All rights reserved

Reprint of: Long-range atmospheric transport of PAHs, PCBs and PBDEs to the central and eastern Mediterranean and changes of PCB and PBDE congener patterns in summer 2010 (Reprinted from Atmospheric Environment, vol 111, pg 51-59)

The central and eastern Mediterranean is a receptor area for persistent organic pollutants (POPs) emitted in western, central and eastern Europe, particularly during summer. Atmospheric concentrations of PCBs, DDXs, PBDEs, penta- and hexachlorobenzene were measured during a ship-borne survey in the summer of 2010. The concentration of PCBs (sum of 7 congeners) was 3.61 (2.08-7.72) pg m(-3), of which 6.7% was associated with the particulate phase. The mean concentration of DDT isomers and their metabolites, DDE and DDD, was 2.60 (0.46-7.60) pg m(-3) (particulate mass fraction theta = 0.097), of penta- and hexachlorobenzene 0.22 (<0.39-2.80) pg m(-3) and 6.29(2.48-24.16) pg m(-3), respectively, and of PBDEs (sum of 8 congeners) 7.31 (2.80-19.89) pg m(-3). The air masses studied had been transported mostly across central Europe, some crossing western Europe. The observed changes of PCB congener patterns along transport routes are in agreement with the perception that the reaction with the OH radical is dominating PCB atmospheric lifetime, and indicate an overestimation of the second order gas-phase reaction rate coefficient of PCB153 with OH by structure-activity relationship. (C) 2015 Elsevier Ltd. All rights reserved

HBCDs in the top predator Greenland shark (Somniosus microcephalus) from Greenland seawaters

Introduction Hexabromocyclododecane (1,2,5,6,9,10-hexabromocyclododecane, HBCD) is a brominated flame retardant (BFR) consisting of 16 possible isomers, three of them (α-, β-and γ-HBCD) are the main components in the commercial mixtures 1. The Greenland shark Somniosus microcephalus is a top predator and the long-lived vertebrate known, with an average life span of at least 272 years 2. In general, its biology and ecotoxicology are poorly understood 3. Considering that S. microcephalus is an opportunistic, extremely long-lived and slow-growing top-predator 2 , it is prone to bioaccumulate high concentrations of organohalogen contaminants (OCs) such as BFRs in its tissues 3. The aims of this study were to: (a) assess the HBCD concentrations in muscle samples of S. microcephalus from Greenland seawaters and (b) to investigate whether HBCD concentration is correlated to lipid content, gender, and age

Nitro- and oxy-PAHs in grassland soils from decade-long sampling in central Europe

Long-term exposure to polycyclic aromatic hydrocarbons (PAHs) and their nitrated (NPAHs) and oxygenated (OPAHs) derivatives can cause adverse health effects due to their carcinogenicity, mutagenicity and oxidative potential. The distribution of PAH derivatives in the terrestrial environment has hardly been studied, although several PAH derivatives are ubiquitous in air and long-lived in soil and water. We report the multi-annual variations in the concentrations of NPAHs, OPAHs and PAHs in soils sampled at a semi-urban (Mokrá, Czech Republic) and a regional background site (Košetice, Czech Republic) in central Europe. The concentrations of the Σ18NPAHs and the Σ11+2OPAHs and O-heterocycles were 0.31 ± 0.23 ng g−1 and 4.03 ± 3.03 ng g−1, respectively, in Košetice, while slightly higher concentrations of 0.54 ± 0.45 ng g−1 and 5.91 ± 0.45 ng g−1, respectively, were found in soil from Mokrá. Among the 5 NPAHs found in the soils, 1-nitropyrene and less so 6-nitrobenzo(a)pyrene were most abundant. The OPAHs were more evenly distributed. The ratios of the PAH derivatives to their parent PAHs in Košetice indicate that they were long-range transported to the background site. Our results show that several NPAHs and OPAHs are abundant in soil and that gas-particle partitioning is a major factor influencing the concentration of several semi-volatile NPAHs and OPAHs in the soils. Complete understanding of the long-term variations of NPAH and OPAH concentrations in soil is limited by the lack of kinetic data describing their formation and degradation.Max-Planck-Gesellschaft http://dx.doi.org/10.13039/501100004189Czech Science FoundationMinisterstvo Školství, Mládeže a Tělovýchovy (CZ)Ministerstvo Školství, Mládeže a Tělovýchovy http://dx.doi.org/10.13039/501100001823Českomoravský Cement a.s.Horizon 2020 http://dx.doi.org/10.13039/501100007601Max Planck Institute for Chemistry (2

Uncertainties in monitoring of SVOCs in air caused by within-sampler degradation during active and passive air sampling

Degradation of semivolatile organic compounds (SVOCs) occurs naturally in ambient air due to reactions with reactive trace gases (e.g., ozone, NOx). During air sampling there is also the possibility for degradation of SVOCs within the air sampler, leading to underestimates of ambient air concentrations. We investigated the possibility of this sampling artifact in commonly used active and passive air samplers for seven classes of SVOCs, including persistent organic pollutants (POPs) typically covered by air monitoring programs, as well as SVOCs of emerging concern. Two active air samplers were used, one equipped with an ozone denuder and one without, to compare relative differences in mass of collected compounds. Two sets of passive samplers were also deployed to determine the influence of degradation during longer deployment times in passive sampling. In active air samplers, comparison of the two sampling configurations suggested degradation of particle-bound polycyclic aromatic hydrocarbons (PAHs), with concentrations up to 2× higher in the denuder-equipped sampler, while halogenated POPs did not have clear evidence of degradation. In contrast, more polar, reactive compounds (e.g., organophosphate esters and current use pesticides) had evidence of losses in the sampler with denuder. This may be caused by the denuder itself, suggesting sampling bias for these compounds can be created when typical air sampling apparatuses are adapted to limit degradation. Passive air samplers recorded up to 4× higher concentrations when deployed for shorter consecutive sampling periods, suggesting that within-sampler degradation may also be relevant in passive air monitoring programs