Ambient air quality and drug aftermaths of the Notte Bianca (White Night) holidays in Rome

Abstract

The environmental impact of Notte Bianca (White Night) holidays held during September 2007 in Rome, Italy, was investigated by measuring aerial concentrations of several genotoxic, psychotropic or source-dependent organic pollutants. Chemical characterization of airborne particulates collected concurrently at Montelibretti RM (semi-rural locality lying ∼30 km NE of Rome centre) was used as a reference. n-Alkanes, polynuclear aromatic hydrocarbons (PAH) and nitrogen/oxygen-containing polyaromatic compounds (PAC) did not seem to undergo important enhancements during the holiday celebration, whilst recreational drugs peaked downtown (87 vs 41 pg m⁻³, on the average, of cocaine, and 5.0 vs. 2.6 ng m⁻³ of nicotine). By contrast, a simultaneous raising of aerial drugs was not detected at Montelibretti.

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Introduction

On 27^th September 2003, the Municipality of Rome, Italy celebrated its first late summer feast,¹ introduced some years before in Berlin (1997: Lange Nacht den Museen), and Paris (2002: Nuit Blanche).^2,3 The success of that event drove the municipality to replicate it every year and increase the number of cultural and entertainment offers (concerts, museums guided tours, shows, libraries, sport facilities, green parks and shops opening). In 2007 the nights were doubled, and the celebrations took place on both 7^th and 8^th September. More than 2.5 million people attended.⁴ The city management board made efforts to warrant the best success of the event and to minimize possible adverse effects on the citizens. For instance, the improvement of train, bus and taxi services was planned to prevent the rushed recourse to use of private vehicles; the numerous shows and events required the increase of the city cleaning service (ca. 2.5 × 10⁸ g of rubbish and urban refuses were produced, i.e. ca. 20% more than the daily average of Rome).⁵ Furthermore, during these days, police controls and first aid services for drug and alcohol were intensified.

On the other hand, no information was available concerning the consequences of the Notte Bianca holidays on the ambient air quality. This was the rationale why a short measurement campaign was conducted in downtown Rome and its outskirts, by using organic particulate compounds as tracers. Measurements were made before, during and after the event. Aiming at obtaining information about the source impact and the particulate effects on the human health, our study was focussed onto conventional pollutants, including polynuclear aromatic hydrocarbons PAH, polar nitrogen/oxygen-containing polyaromatic compounds PAC and n-alkanes, as well as onto psycho-active compounds like nicotine, caffeine and cocaine. At this regard, it is well known that high percentages of the atmospheric particulate mutagenicity and carcinogenity are associated to its organic fraction. Toxicity seems to be enhanced by the burden of PAH (30∼50% of the whole mutagenic activity of the particulate organic extract), but especially by oxy- and nitro-PAC.^6–8 Despite that, according to Italian regulation, only benzo(a)pyrene is submitted to limits for its concentration in the air (yearly average equal to 1 ng m⁻³).⁹ No regulation exists for individual PAH at workplaces, while the threshold limit values (TLV) for total PAH is included in the value established for coal tar pitch volatiles (0.2 mg m⁻³).¹⁰ A limit exists for nicotine concentration in indoor air (0.5 mg m⁻³),¹⁰ while many organic contaminants quoted in legislations referring to source emissions are not taken in account as regards atmosphere (e.g. chlorinated dioxins). Although not toxic, n-alkanes are of environmental concern and were investigated as suitable to discriminate biogenic from anthropogenic emission,¹¹ so the modulation of their percent profile in air provided information about the relative importance of the sources. Nicotine and caffeine were regarded as tracers for tobacco smoking and food cooking, respectively. Finally, in agreement with its recent discovery in the air of Italian cities,¹²cocaine was studied to confirm the behaviour observed in river waters. There, higher burdens of drugs were found during weekends, when the prevalence of psychotropic substances increased.^13–15 We suspected that the concentration of events during Notte Bianca stimulated the recourse to psychotropics.

Experimental

Sampling locations, time and conditions

Airborne particulate composition was investigated at two locations. The first site was the green garden of Villa Ada, (i.e. the largest city garden of downtown Rome), and the second was Montelibretti, a semi-rural zone served by train and highway facilities lying ∼30 km NE of Rome centre.¹⁶ The collection of airborne particulates was made daily, from September 4^th up to September 17^th 2007. Aerosols were collected by using two twin Hydra medium-volume samplers (FAI Instruments, Palombara Sabina RM, Italy). Each instrument was equipped with a pair of PM₁₀ particle inertial impactors, and met the requirements of the European Reference Method for PM₁₀,^17,18e.g. ± 2% accuracy, 2.3 m³ h⁻¹ flow rate. Atmospheric particulates were collected on PTFE membranes, 47 mm o.d., 2 µm pore size¹⁸ (Pall Corp., Ann Arbor, Michigan, USA), which provided high filtration efficiency (> 99%) for submicron particles. Samplings started at 00:00 h and lasted 24 h.

Airborne particulate analysis

Before using, particulate filters were baked 12 h at 70 °C in a clean oven and equilibrated at ambient temperature (20 ± 2 °C) in a dryer, then they were individually sealed in polyethylene boxes. After sample collection, filters were sealed again, wound with aluminium foils and stocked at −25 °C. Chemical characterization of aerosols was made by applying the procedure described elsewhere,¹⁹ with the only important variation of gathering and running together three daily pairs of samples in order to reach the method reliability requirements. Briefly, airborne particulates were spiked with internal reference compounds solution, soxhlet extracted with dichloromethane and acetone (4 : 1 in volume, 16 h, 120 mL), reduced to close dryness, and separated through neutral alumina column chromatography. Three fractions were eluted with isoctane, isoctane/dichloromethane (60:40 in volume), and dichloromethane/acetone (50 : 50), in sequence, which comprised n-alkanes, PAH and Nitro-PAH, and PAC and drugs, respectively. The groups of compounds investigated were: i) the C₁₈ to C₃₆n-alkanes; ii) PAH congeners with molecular weights ranging from 202 (fluoranthene, pyrene) to 278 [dibenz(a,h)anthracene]; iii) Nitro-PAH from nitrofluorene to nitrochrysene; iv) a set of PAC comprising acridine, carbazole and benzoacridines, anthrone, anthraquinone and benzanthrone; and v) the following drugs and metabolites: nicotine, caffeine, cotinine, cocaine, methadone, cocaethylene and heroin.

Identification and quantification of target compounds were performed by HRGC-MS (EI/SIM) detection, except n-alkanes analyzed by flame ionization (FID). The list of reference compounds included perdeuterated n-hexadecane, n-eicosane, n-tetracosane and n-triacontane, phenanthrene-d₁₀, fluoranthene-d₁₀, pyrene-d₁₀, chrysene-d₁₂, perylene-d₁₂, benzo(ghi)perylene-d₁₂, 1-nitronaphthalene-d₇, 1-nitropyrene-d₉, nicotine-d₄, caffeine-d₃, cocaine-d₃, heroin-d₉, methadone-d₃; all of them were provided by Cerilliant (Chemical Research 2000, Rome, Italy) as pure (∼99%) standards or solutions in methanol (each at 1.0 or 0.1 µg mL⁻¹). Native standards (by Accustandard) were provided by Superchrom, Milan, Italy, except drugs, purchased again from Chemical Research. Sample residues were dissolved in toluene and injected into the gas chromatograph in split-less mode through a programmed-temperature vaporizer. The instrument was a DSQ/GC Trace system (Thermo, Rodano MI, Italy) served by the Excalibur dedicated software. Analytes were separated in temperature gradient (80 °C∼290 °C) through a RTX-type capillary column (Restek, provided by Superchrom; 30 m, 0.25 mm, 0.3 µm), using helium (0.7 mL min⁻¹) as carrier gas. Quantitative evaluations were made according to the isotopic dilution method, by comparing each analyte to the closest reference congener in the chromatogram. The limits of quantification (LOQ) were 20∼50 pg m⁻³ for n-alkanes, 1 to 4 pg m⁻³ for PAH, 3∼8 pg m⁻³ for Nitro-PAH, 30 pg m⁻³ for nicotine and heroin, and 5 pg m⁻³ for the other compounds. As regards psychotropics, the procedure provided only qualitative information about tetrahydrocannabinol, cannabidiol and cannabinol (LOQ ≈ 100 pg m⁻³).²⁰ These compounds could not be analyzed through EI/SIM mode as native; indeed, the derivatization with silyl-donor agents [e.g., heptafluorobenzyl anhydride or N,O-bis(trimethylsilyl)trifluoroacetamide]^21,12 was confirmed to be necessary for the evaluation of these compounds at the low levels they reached in the atmosphere.

Blank filters were analyzed to check for analytical interferences. For this purpose, three pairs of PTFE unexposed filters were subjected to the whole analytical procedure. Only light n-alkanes (≤C₂₃) were found at slight levels that required the blank subtraction from true samples.

Results and discussion

The average concentrations of n-alkanes, PAH, Nitro-PAH and oxygen/nitrogen containing PAC over the entire in-field campaign are shown in Fig. 1a/d. n-Alkanes peaked all-the-time in correspondence of C₂₉ and exhibited the predominance of odd homologues in the range >C₂₅. Benzo(j/k)fluoranthene was the most abundant PAH at both sites, followed by indeno(1,2,3-cd)pyrene and benzo(ghi)perylene.

Fig. 1 Average concentrations of n-alkanes (a), PAH (b), nitro-PAH (c) and PAC (d) in downtown Rome and Montelibretti in September 2007.

The time modulation of total n-alkanes, PAH and Nitro-PAH during the campaign is shown in Table 1 for the two sites. For sake of completeness, the standard deviations (RDS) are also reported. RDS did not exceed 27% for PAH, Nitro-PAH and PAC at Montelibretti, but they reached ∼65%, >100% and 100%, respectively, downtown. RDS of n-alkanes were (∼20 ± 5%) at both locations. Table 1 reports also the values of CPI₂₅ indexes¹¹ and benzo(a)pyrene concentrations. The CPI₂₅ index refers to n-alkanes and allows to evaluate the contribution of biogenic emission to organic particulate, since rates as high as 5∼7 are typical of high vegetation leaf debris whilst rates equal to 1 refer to petrogenic emission.^22,23 During the campaign, benzo(a)pyrene never reached 1.0 ng m⁻³, that is the concentration limit for Italy and Europe. In agreement with most co-pollutants, benzo(a)pyrene did not reach the maximum during the Notte Bianca event. Concerning nitro-PAH, 1-nitropyrene was absent in most samples, while the presence of 2-nitrofluoranthene suggested that most nitro-derivatives derived from oxidation processes of PAH.^24,25 The percent distribution of the Nitro-PAH group at the sites were similar, except one sample downtown (11^th to 13^th September), where very high concentrations of all congeners were detected. As regards oxy-PAC and nitro-PAC, the minimums were recorded during the Notte Bianca at Montelibretti, but not downtown.

Table 1 Total n-alkanes, PAH, benzo(a)pyrene, Nitro-PAH and PAC detected at Villa Ada (Rome) and Montelibretti RM in September 2007. Average O₃ and NO₂ and PM₁₀,²⁷ maximum daily temperature, average wind velocity and prevailing wind direction²⁸ are also reported.^a

Site	Villa Ada garden (downtown Rome)
compounds/days	04–06	07–10	11–13	14–17	ave.	st. dev.
n-alkanes, ng m^−3	26.1	21.9	14.3	21.4	20.9	4.9
CPI25^a	4.4	4.8	2.8	1.5	3.4	1.5
PAH, ng m^−3	2.24	2.50	7.13	2.47	3.59	2.36
benzo(a)pyrene, ng m^−3	0.10	0.14	0.45	0.14	0.21	0.16
Nitro-PAH, ng m^−3	0.71	0.30	2.91	0.27	1.05	1.26
N-PAC, ng m^−3	0.10	0.10	0.10	0.06	0.09	0.02
O-PAC, ng m^−3	0.57	0.18	0.10	0.07	0.23	0.23
O3, µg m^−3	99	107	99	92	99	6
NO2, µg m^−3	47	106	93	89	84	26
PM10, µg m^−3	23.3	25.0	26.3	33.3	27.0	4.4
max. temperature, °C	24	27	27	29	27	2.1
wind speed, km/h	10.0	6.3	6.7	5.5	7.1	2.0
prevailing direction	N	NW	NW	SW

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Site	Montelibretti RM
compounds/days	04–06	07–10	11–13	14–17	ave.	st. dev.
a . * Measured at Bufalotta (see the text).
n-alkanes, ng m^−3	18.1	12	13.1	14.2	14.4	2.7
CPI25^a	5.0	3.6	4.3	3.5	4.1	0.7
PAH, ng m^−3	0.93	1.25	1.15	1.33	1.17	0.17
benzo(a)pyrene, ng m^−3	0.03	0.06	0.04	0.07	0.05	0.01
Nitro-PAH, ng m^−3	0.27	0.20	0.29	0.29	0.26	0.04
N-PAC, ng m^−3	0.13	0.07	0.11	0.13	0.11	0.03
O-PAC, ng m^−3	0.10	0.08	0.10	0.09	0.09	0.01
O3, µg m^−3 *	92	101	95	88	94	5
NO2, µg m^−3 *	43	90	88	79	75	22
PM10, µg m^−3	20.0	23.0	27.0	32.5	25.6	5.4

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The modulations of drugs, in the period investigated, appeared very interesting (see Table 2). In fact, nicotine, caffeine, cotinine and cocaine peaked in correspondence of the Notte Bianca days in downtown Rome, whilst the same pattern was not observed at Montelibretti. By contrast, heroin, methadone and cocaethylene were never found. Cannabinol provided inconsistent results, since it could be detected, but not quantified, solely downtown during the Notte Bianca event.

Table 2 Average aerial concentrations (ng m⁻³) of nicotine, cotinine, caffeine and cocaine recorded in downtown Rome and at Montelibretti in September 2007

Site	Villa Ada garden (downtown Rome)
compounds/days	04–06	07–10	11–13	14–17	ave.	st.dev.
Nicotine	2.43	4.96	3.12	2.37	3.22	1.21
Cotinine	0.05	0.20	0.18	0.13	0.14	0.07
Caffeine	0.21	0.42	0.31	0.26	0.30	0.09
Cocaine	0.022	0.087	0.052	0.048	0.052	0.026

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Site	Montelibretti RM
compounds/days	04–06	07–10	11–13	14–17	ave.	st. dev.
Nicotine	0.50	0.65	0.84	0.87	0.72	0.17
Cotinine	0.25	0.22	0.15	0.57	0.30	0.19
Caffeine	0.15	0.19	0.48	0.46	0.32	0.18
Cocaine	0.006	0.019	0.013	0.024	0.015	0.008

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Some insights about the contaminant behaviours could be drawn by looking to meteorological situation dominating the region during the period. The days preceding the holiday event were characterized by strong vertical mixing of the earth boundary layer. Atmospheric stability conditions started during the Notte Bianca and continued in the subsequent days causing accumulation of pollutants at the ground.²⁶ This behaviour is fairly depicted by patterns of NO₂ concentration, maximum daily temperature (T_M), average wind velocity (ū), and prevailing wind direction (u_M) recorded at Villa Ada.^27,28 Even more evident was the modulation of PM₁₀ vs. ambient temperature, and wind velocity. At Bufalotta,²⁷ca. mid way between Villa Ada and Montelibretti, both O₃ and NO₂ concentrations were in agreement with those found downtown. In particular, O₃ and NO₂ reached their maximums during and just after the Notte Bianca holidays, whilst PM₁₀ peaked at the third sampling. For that concerns drugs, in downtown Rome cocaine reached 87 pg m⁻³ during the Notte Bianca weekend, while was equal to 41 ± 16 pg m⁻³ on the other days. Similarly, nicotine raised from 2,640 ± 420 pg m⁻³ up to 5,000 pg m⁻³, and caffeine from 260 (±46) pg m⁻³ up to 420 pg m⁻³. It is worth remarking that whilst in Milan the drug abuse was found to peak in the weekends,¹³ we did not observe that behaviour between Friday 14^th and Monday 17^th September 2007. Less evident was the increase of cotinine (from 121 ± 60 pg m⁻³ to 223 pg m⁻³). Unlike downtown Rome, at Montelibretti, the maximum concentrations of drugs were reached with the last sampling made in correspondence of the weekend following the event, when well established stability conditions were also developed.

Conclusions

The celebration of the Notte Bianca holidays in Rome during September 2007 caused a detectable increase of drugs, cocaine in particular, associated with airborne particulates. Neither did other organic pollutants present similar behaviours downtown, nor were drug increases found concurrently in the outskirts. Two important suggestions were also drawn. First, cocaine survives enough time in the air to be collected and measured; on the other hand it does not correlate with the major pollutants or atmospheric stability, thus its behaviour is peculiar. Second, cocaine seems to respond quickly to the drug abuse rate. In fact, the quick variations observed in airborne particulate seem consistent with a proportionality between the amount of drug consumed day-by-day and the concurrent aerial concentration. This suggests that specific information would be drawn by characterizing airborne particulates during similar holiday events, in the perspective of preventing and contrasting the illicit substances abuse, as well as preserving the wellbeing of citizens.

Acknowledgements

The authors thank Italian Ministry of University and Research MIUR granting this study in the frame of the FIRB-2001 Program. They are also indebted to the IIA-CNR team leaded by Dr Antonio Febo, which kindly provided the plots of meteorological evolution during the sampling period.

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