Laboratory and on-road testing for brake wear particle emissions: a review.

Brake wear emission is a significant contributor to vehicle-related particulate matter, especially in areas with high traffic density and braking frequency. Only recently, non-exhaust emissions from car brake wear have been regulated under Euro 7 regulation, which introduces emission limits for both brake and tires. It also introduces a standard brake particle assessment procedure which includes sampling procedure and measurement techniques defined in the Global Technical Regulation on brakes from light-duty vehicles up to 3.5 t. Over the years, various experimental setups have been tried leading to non-comparable results. The brake wear particle emissions, expressed as emission factors, are mostly estimated as particle mass or particle number and described using different units (e.g., mg/stop brake, mg/km brake; particle number/cm3) making the comparison between studies very difficult. The aim of the present literature review is to present the state-of-the-art of different experimental methods tuned for assessing brake wear emissions, including electric vehicles. The experiments are carried in close, semi-closed, and open systems, and depending on the experimental design, different sampling methods are applied to reduce particle transport loss and guarantee the efficiency of the particle sampling. Driving condition (e.g., speed and applied pressure), formulation of brake materials, and friction temperature have been found to strongly affect the emission characteristics of brake particles, and this needs to be considered when designing study procedures. The findings reported in this review can be beneficial to policy makers and researchers.

Occurrence of per- and polyfluorinated alkyl substances in wastewater treatment plants in Northern Italy.

Wastewater treatment plants are known to be relevant input sources of per- and polyfluoroalkyl substances (PFAS) in the aquatic environment. This study aimed to investigate the occurrence, fate, and seasonal variability of twenty-five PFAS in four municipal wastewater treatment plants (WWTP A, B, C, and D) surrounding the city of Milan (Northern, Italy). Composite 24-h wastewater samples were collected in July and October 2021 and May and February 2022 from influents and effluents of the four WWTPs. PFAS were detected at concentrations ranging between 24.1 and 66.9 µg L-1 for influent and 13.4 and 107 µg L-1 for effluent wastewater samples. Perfluoropentanoic acid was the most abundant (1.91-30.0 µg L-1) in influent samples, whereas perfluorobutane sulfonic acid predominated (0.80-66.1 µg L-1) in effluent samples. In sludge, PFOA was detected in plant A at concentrations in the range of 96.6-165 ng kg-1 dw in primary sludge samples and 98.6-440 ng kg-1 dw in secondary treatment sludge samples. The removal efficiency of total PFAS varied between 6 % and 96 %. However, an increase of PFAS concentrations was observed from influents to effluents for plant D (during July and October), plant A (during October and May), and plant C (during May) indicating that biotransformation of PFAS precursors can occur during biological treatments. This was supported by the observed increase in concentrations of PFOA from primary to secondary treatment sludge samples in plant A. Moreover, the plant operating at shorter hydraulic retention times (plant D) showed lower removal efficiency (<45 %). Seasonal variation of PFAS in influent and effluent appears rather low and more likely due to pulse release instead of seasonal factors.

Extractable denuders for selective sampling of vapour phase organics in the atmosphere.

Extractable denuders were designed to collect trace atmospheric semivolatile organic compounds with high volume (38.30 and 200 L/ min) samplers. Denuders were made of multichannel ceramic support coated with sodium silicate and functionalised with phenyl moieties. Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, polychlorinated dibenzodioxins and polychlorinated dibenzofurans and chlorobenzenes in ambient air of a sub-urban area of Monterotondo, Italy, were sampled. Samplings were of 24 h, 48 h and 1 week period. Precision was determined using field triplicates and compared to the conventional high volume sampler methods. The fraction of analytes in the particle phase measured with the filter/ PUF system ranged from 0.2 % for naphthalene to 98.5 % for benzo(ghi)perylene; this fraction measured with the denuder ranged from 0.5 % for naphthalene to 99.0 % for benzo(ghi)perylene. A paired t-test indicated that these values were significantly (t = 3.58, P < 0.01) higher for the denuder. Results showed good repeatability (0.4-4.6 %), sampling efficiency (>99 %) and good capacity as variations in experimental efficiency were not observed also for longer (1 week) period sampling. As significant changes in efficiency were observed (0.7-5.6 %), the developed denuder cannot be reused more than once. However, it is possible to regenerate the denuder with a new silanization step. A good linear correlation was found plotting the vapour/particle distribution ratio versus the vapour pressure (R2 ranged between 0.59 and 0.84) and versus the octanol/air partition coefficient (R2 ranged between 0.85 and 0.88) of each selected SVOCs, in good agreement with the theoretical models for partitioning of SVOCs.

Pharmaceuticals and other contaminants in waters and sediments from Augusta Bay (southern Italy).

The contamination by pharmaceuticals products (PPs) in the marine environment is particularly relevant where wastewater treatment of urban areas on land is lacking. However, the number of studies focused on description of sources and fate of PP molecules in the marine environment remains still limited. In this study, the occurrence of 46 PPs was investigated in the marine and coastal-marine system (waters and sediments) of Augusta Bay (central Mediterranean Sea). This area is highly affected by industrial pollution and urban discharges (without wastewater treatment) and thus represents a 'natural laboratory' for exploring dynamics of multi-mixture contaminants in the marine environment. The study area is also part of the sub-region 'Central Mediterranean Sea' of the Marine Strategy Framework Directive and therefore offers an important reference site for exploring the distribution modes of PPs in the central Mediterranean Sea. In this work, samples of seawater, sediment, untreated wastewater, and marine receiving water were analysed using mass spectrometry with a target analysis for PPs and a suspect screening analysis for the presence of other contaminants. PPs concentration ranges were: 2426-67,155 ng/L for untreated wastewaters, 550-27,889 ng/L for marine receiving waters and 12-281 ng/L for seawaters. The highest concentrations were measured for the antibiotics, anti-inflammatories, cardiovascular and antihypertensive therapeutic classes. Likewise, sediments collected from untreated wastewater sewers resulted more contaminated. Ionic, non-ionic surfactants and personal care products were the most abundant compounds found in waters and sediments by suspect screening analysis. The risk associated with PPs contamination for aquatic organisms was relatively high in samples of marine receiving waters of the bay (with a risk quotient value up to 33,599). The levels of PPs in seawater and sediment compartments were generally not hazardous (RQ < 0.01), except for estrone with a calculated RQ = 2775.

Toxic heritage: Maternal transfer of pyrethroid insecticides and sunscreen agents in dolphins from Brazil.

Pyrethroids (PYR) and UV filters (UVF) were investigated in tissues of paired mother-fetus dolphins from Brazilian coast in order to investigate the possibility of maternal transfer of these emerging contaminants. Comparison of PYR and UVF concentrations in maternal and fetal blubber revealed Franciscana transferred efficiently both contaminants to fetuses (F/M > 1) and Guiana dolphin transferred efficiently PYR to fetuses (F/M > 1) different than UVF (F/M < 1). PYR and UVF concentrations in fetuses were the highest-ever reported in biota (up to 6640 and 11,530 ng/g lw, respectively). Muscle was the organ with the highest PYR and UVF concentrations (p < 0.001), suggesting that these two classes of emerging contaminants may have more affinity for proteins than for lipids. The high PYR and UVF concentrations found in fetuses demonstrate these compounds are efficiently transferred through placenta. This study is the first to report maternal transfer of pyrethroids and UV filters in marine mammals.

Development of a liquid chromatography-electrospray chemical ionization tandem mass spectrometry analytical method for analysis of eleven hydroxylated polybrominated diphenyl ethers.

Recently, hydroxylated polybrominated diphenyl ethers (OH-PBDEs) have emerged as environmentally relevant pollutants due to recent reports of their natural production and metabolism. Recent mechanistic studies in human and rats have shown that some OH-PBDEs are more potent than parent compounds (PBDEs) and may contribute substantially to neurodevelopmental disorders by direct neurotoxicity, or indirectly through altered thyroid disruption. However, analytical methodologies for determination of OH-PBDEs are currently limited. In this study a robust liquid chromatography-electrospray tandem triple quadrupole-linear ion trap mass spectrometer (LC-ESI-QqLIT-MS-MS) in negative mode method was developed for the determination of eleven OH-tri- to OH-hexa-PBDEs. Two different columns were tested and compared for chromatographic separation: a C18 BetaBasic and a Purospher STAR RP 18, working at pH 8 and 10, respectively. Mobile phase (acetonitrile:water) was optimized by changing the pH of the aqueous phase and the concentration of the organic modifier (methanol). The MS-MS parameters (declustering potential (DP), collision energy (CE) and cell exit potential (CXP)) were optimized. Selected reaction monitoring (SRM) was used in order to increase sensitivity. Two SRM transitions ([M-H](-)>[Br](-)) were selected for each OH-PBDE, one for quantification and the second one for confirmation. Under the optimized conditions, the instrumental limits of detection were between 0.17 and 0.72injectedpg. The method provided good linearity (r>0.99 for a concentration range of 0.30-100ng/mL), accuracy and precision (%Dev and %RSD≤20% for intra- and inter-assays).

Biotransformation of BDE-47 to potentially toxic metabolites is predominantly mediated by human CYP2B6.

BACKGROUND: Previous studies have indicated that cytochrome P450s (CYPs) are involved in the metabolism of polybrominated diphenyl ether (PBDE) flame retardants in humans, resulting in the formation of hydroxylated PBDEs (OH-PBDEs) that are potentially more toxic than the parent PBDEs. However, the specific enzymes responsible for the formation of OH-PBDEs are unknown. OBJECTIVES: The purposes of this study were to characterize the in vitro metabolism of 2,2´,4,4´-tetrabromodiphenyl ether (BDE-47) by human liver microsomes (HLM) and recombinant human CYPs, and to identify the CYP(s) that are active in the oxidative metabolism of BDE-47. METHODS: Recombinant human CYPs (CYP1A1, 1A2, 1B1, 2A6, 2B6, 2C8, 2C9, 2C19, 2D6, 2E1, and 3A4) were incubated with BDE-47 (20 µM), and the metabolites were measured and characterized using gas chromatography with tandem mass spectrometry (GC-MS/MS). For kinetic studies, CYP2B6 and pooled human liver microsomes (HLMs) were incubated with BDE-47 (0-60 µM). RESULTS: CYP2B6 was the predominant CYP capable of forming six OH-BDEs, including 3-OH-BDE-47, 5-OH-BDE-47, 6-OH-BDE-47, 4-OH-BDE-42, 4´-OH-BDE-49, and a metabolite tentatively identified as 2´-OH-BDE-66. On the basis of full-scan GC-MS analysis, we hypothesized the formation of two other metabolites: di-OH-tetra-BDE and di-OH-tetrabrominated dioxin. In kinetic studies of BDE-47 metabolism by CYP2B6 and pooled HLMs, we found Km values ranging from 3.8 to 6.4 µM and 7.0 to 11.4 µM, respectively, indicating the high affinity toward the formation of OH-BDEs. CONCLUSION: Our findings support a predominant role of CYP2B6 in the metabolism of BDE-47 to potentially toxic metabolites, including a hypothesized di-OH-tetrabrominated dioxin metabolite. These results will assist future epidemiological studies investigating the potential of PBDEs and their metabolites to produce neurobehavioral/neurodevelopmental disorders.

Population growth rate responses of Ceriodaphnia dubia to ternary mixtures of specific acting chemicals: pharmacological versus ecotoxicological modes of action.

When considering joint toxic apical effects at higher levels of biological organization, such as the growth of populations, the so-called pharmacological mode of action that relies on toxicological mechanistic effects on molecular target sites may not be relevant. Such effects on population growth rate will depend on the extent to which juvenile and adult survival rates and production rates (juvenile developmental rates and reproduction) are affected by toxic exposure and also by the sensitivity of population growth rates to life-history changes. In such cases, the ecotoxicological mode of action, defined as the crucial life-history trait processes and/or xenobiotic-life-history trait interactions underlying a toxicological effect on population growth rate, should be considered. Life-table response experiments with the crustacean Ceriodaphnia dubia exposed to single and ternary mixtures of nine compounds were conducted to test the hypothesis that joint effects on population growth rates could be predicted from the mixture constituent ecotoxicological mode of action. Joint effects of mixtures containing pharmacologically dissimilar compounds (cadmium, λ-cyhalothrin, and chlorpyrifos) that differentially affected life-history traits contributing to population growth rates were accurately predicted by the independent-action concept. Conversely, the concentration-addition concept accurately predicted joint effects of two different mixtures: one containing pharmacologically similar acting pyrethroids that also affected similarly life-history traits, the other one that included pharmacologically dissimilar compounds (3,4-dichloroaniline, sodium bromide, and fenoxycarb) acting mainly on reproduction rates. These results indicate that when assessing combined effects on population growth rate responses, selection of mixture toxicity conceptual models based on the ecotoxicological mode of action of mixture constituents provided more accurate predictions than those based on the pharmacological mode of action.

Pyrethroids: a new threat to marine mammals?

The present study constitutes the first investigation to demonstrate pyrethroid bioaccumulation in marine mammals, despite the assumption that these insecticides are converted to non-toxic metabolites by hydrolysis in mammals. Twelve pyrethroids were determined in liver samples from 23 male franciscana dolphins from Brazil. The median concentration values for total pyrethroids were 7.04 and 68.4 ng/g lw in adults and calves, respectively. Permethrin was the predominant compound, contributing for 55% of the total pyrethroids. Results showed a distinct metabolic balance of pyrethroids through dolphin life. High loads are received at the beginning of their lives and, when they reach sexual maturity, these mammals seem to degrade/metabolize pyrethroids. Maternal transfer of these compounds was also evaluated through the analysis of breast milk and placenta samples. Pyrethroids were detected in both matrices, with values between 2.53-4.77 ng/g lw and 331-1812 ng/g lw, respectively. Therefore, for the first time, a study shows mother-to-calf transfer of pyrethroids by both gestational and lactation pathways in dolphins.

Pyrethroids in human breast milk: occurrence and nursing daily intake estimation.

There is an assumption that pyrethroid pesticides are converted to non-toxic metabolites by hydrolysis in mammals. However, some recent works have shown their bioaccumulation in human breast milk collected in areas where pyrethroids have been widely used for agriculture or malaria control. In this work, thirteen pyrethroids have been studied in human breast milk samples coming from areas without pyrethroid use for malaria control, such as Brazil, Colombia and Spain. The concentrations of pyrethroids ranged from 1.45 to 24.2 ng g⁻¹ lw. Cypermethrin, λ-cyhalothrin, permethrin and esfenvalerate/fenvalerate were present in all the studied samples. The composition of pyrethroid mixture depended on the country of origin of the samples, bifenthrin being the most abundant in Brazilian samples, λ-cyhalothrin in Colombian and permethrin in Spanish ones. When the pyrethroid concentrations were confronted against the number of gestations, an exponential decay was observed. Moreover, a time trend study was carried out in Brazil, where additional archived pool samples were analyzed, corresponding to years when pyrethroids were applied for dengue epidemic control. In these cases, total pyrethroid levels reached up to 128 ng g⁻¹ lw, and concentrations decreased when massive use was not allowed. Finally, daily intake estimation of nursing infants was calculated in each country and compared to acceptable WHO levels. The estimated daily intakes for nursing infants were always below the acceptable daily intake levels, nevertheless in certain samples the detected concentrations were very close to the maximum acceptable levels.

Pyrethroid use-malaria control and individual applications by households for other pests and home garden use.

Presence of pyrethroid insecticides in human breast milk and in thatch wall material of dwellings from Southern Africa subtropical area (Manhiça, Mozambique) was investigated to assess potential pyrethroid route of human exposure. Human breast milk samples were collected during 2002 when pyrethroids were widely used as insecticides for mosquito bed nets in Mozambique for malaria control. The median concentration value of total pyrethroids ranged between 87 and 1200ng/glw, with λ-cyhalothrin being the most predominant pyrethroid in human breast milk contributing for 35% of the total amount. Moreover, and for the first time, an isomer-specific enrichment was found in human breast milk, showing a selective isomeric accumulation or metabolism in the human body. Based on the calculated pyrethroid concentrations in human breast milk, the daily ingestion rate of pyrethroid was estimated. The nursing infant dietary intake ranged from 0.67 to 9.0µg(kg of body weight)(-1)day(-1). In addition, thatch materials collected after the reintegration of dichlorodiphenyltrichloroethene (DDT) as insecticide residual spraying (IRS) in Mozambique, showed the presence of pyrethroids with concentration values ranging between 6.9 and 700ng/gdw. In thatch material as well as in human breast milk, pyrethroid contamination was mainly attributed to the agriculture usage of this insecticide knowing that agriculture represent the 80% of the economy in Mozambique. However, a possible usage of this insecticide as IRS in Mozambique cannot be excluded despite their low efficiency for malaria control. The continued use of these compounds (both for agriculture and malaria prevention) and the ingestion rates calculated from the breast milk concentrations indicate that these insecticides cannot be overlooked for the assessment of the lactation risks of breastfeeding infants from the Manhiça region.

Polycyclic aromatic hydrocarbons and polychlorinated biphenyls in the harbour of Naples (Southern Italy): time and spatial distribution patterns.

Seventeen parent polycyclic aromatic hydrocarbons (PAHs) and 38 congeners of polychlorinated biphenyls were measured at five different sediment depths (between the surface and ~300 cm below the seafloor) at 160 sites in Naples harbour. Total PAH (ΣPAH) and PCB (ΣPCB) concentrations ranged between 0.012-21.73( - )nd 0.001-0.222 mg kg(-1), respectively. For PAHs, an evident and progressive decrease in concentration with depth documents the effects of a more intense anthropic impact of this group of pollutants in the recent period. A selected number of PAH isomer pairs (phenanthrene/anthracene, fluoranthene/pyrene and benzo(a)anthracene/crysene) were used to distinguish between contaminants of pyrolitic and petrogenic origin. More than 90% of PAHs present at the different depths of the studied sediments indicate pyrolitic industrial origins. On the other hand, relatively high concentrations of three- and four-ring PAHs suggest a limited contribution of vehicular emissions to the contamination of sediments. An unexpected and systematic increase of ΣPCB concentration, exceeding values approved by international regulations, was found in the studied sediments, testifying to the uncontrolled discharge to the studied area from industrial and commercial activity on nearby land. Ecotoxicological risk levels calculated for PAHs suggests a relatively elevated level of toxicity in surface sediments decreasing with depth and very low toxicity values associated to PCB toxicity.

Utility of benthic foraminifera for biomonitoring of contamination in marine sediments: a case study from the Naples harbour (Southern Italy).

We propose a detailed investigation on the distribution patterns of the benthic foraminiferal assemblage and their predominant species in the highly contaminated marine sediments of the Naples harbour. Combined use of multivariate canonical, cluster and principal component analysis in a proper geostatistic framework provided an appropriate approach to explore the role played by a number of contaminants (heavy metals, polycyclic aromatic hydrocarbons, volatile organic compounds, heavy hydrocarbons, PCBs) and different physical parameters (grain size, pH, redox potential, total organic carbon) on the spatial distribution of the benthic foraminiferal assemblage and its single species. Obtained results provide evidence for a high and systematic non-linear response of the biota to the effects of contamination of the different classes of pollutants. The reduced number of specimens per sample, their small dimensions and low diversity, testify the negative effects of a highly contaminated environment. For this reason, it appears very difficult to clearly identify a differential sensitivity of different benthic species to single classes of contaminants. In particular, in addition to a number of case studies which invoked a key role of the heavy metals in the control of the distribution patterns of the benthic foraminifera in the marine environment, the results presented here underline an important effect of some classes of organic compounds (particularly the volatile organic compounds) on the distribution patterns of the benthic assemblage. However, the obtained results demonstrate that any kind of oversimplification would unquestionably cancel the strong complexity of the biotic response to combined effects of different coexisting contaminants.

Heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in surface sediments of the Naples harbour (southern Italy).

The Naples's harbour is one of the largest and most important commercial and tourist port of the Mediterranean basin. It is located on the southeast coast of Italy and receives industrial and municipal wastewaters from the city of Naples. Due to its social and economic impact, a comprehensive assessment of levels and sources of contamination of bottom sediments in this area of the Mediterranean basin is essential to identify potential danger due to mobilization of contaminants produced by managing of the same sediments. In this study, superficial sediments collected from 189 sampling sites were analyzed for grain size, heavy metals (Cr, Cu, Ni, Pb, V, Zn, Co, Sn, Cd, Hg, As, Al and Fe), 16 priority polycyclic aromatic hydrocarbons (PAHs) and perylene and 38 individual polychlorinated biphenyl (PCB) congeners. Compared to the estimated local background, Cu, Zn, Pb, Cd, Sn and Hg show enrichment factors >3 and only Hg evidences a median value higher than the NOAA (effects range - median) guidelines. Principal component analysis allowed us to clearly discriminate two areas mainly affected by heavy metals contamination and influenced by different sources related to industrial, commercial and/or urban activities. Priority PAHs are predominantly represented by three-five-ring compounds with concentrations ranging between 9 and 31774 ng g(-1) and frequently higher than the NOAA ER-M index. A prevalent pyrolitic origin of PAH was assessed on the basis of the relative abundance of the different congeners and selected isomer ratios. The concentrations of PCBs, as sum of the 38 congeners, ranged from 1 to 899 ng g(-1), with a predominance of highly chlorinated (tetra- and penta-chlorobiphenyls) congeners. WHO-TEQ values, calculated for the PCDD-like PCB congeners, suggest a relatively high level of toxicity. Generally, the concentration of PAHs and PCBs were higher near the sites of intense industrial, shipping and/or commercial activities suggesting a direct influence of these sources on the pollutant distribution patterns.