Atmospheric BTX and polyaromatic hydrocarbons in Rio de Janeiro, Brazil

Polycyclic aromatic and monoaromatic (benzene, toluene and xylene, or BTX) hydrocarbons were monitored in Rio de Janeiro, Brazil, during the summer of 1998/1999. The levels of these aromatic chemicals decreased with distance from main roads, indicating mobile sources are the main pollutant emitters in this Latin American city. Benzo[ghi]perylene/indeno[1,2,3-cd]pyrene and benzene/toluene ratios corroborate this idea. However, higher benzene/toluene ratios at one of the major access routes into the city suggest pollutant inputs from a nearby refinery. Literature data were reviewed in order to outline differences and similarities among sources and levels of aromatic pollutants in large urban agglomerations worldwide. Concentrations of benzo[a]pyrene and benzene, which are well-known carcinogenic chemicals, were relatively low in Rio de Janeiro. This fact was attributed to specific atmospheric conditions during the tropical summer and differences in vehicle fuel composition.     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.     

Brazilian Oil Spills Chemical Characterization--Case Studies

In the last decade, PETROBRAS has experienced some significant oil spills cases and the PETROBRAS Research Center has played an important role in the company emergency response program by characterizing the spilled oil, monitoring the affected ecosystem, determining the fate of the oil in the environment, and, subsequently, helping the company in assessing the environmental damage. This paper presents the use of advanced chemical analytical techniques (GC/FID, P&T/GC/PID and GC/MS) in some Brazilian oil spill studies in order to determine fractions and individual petroleum hydrocarbons in different matrices such as water, groundwater, sediment, sand, fish and the spilled oil itself. The spill studies encompassed crude and fuel oil releases on land and coastal ecosystems, related to the incidents in Guanabara Bay (Rio de Janeiro), Barigui and Iguassu Rivers (Parana) and Sao Sebastiao Channel (Sao Paulo). Total petroleum hydrocarbons (TPH), n -alkanes, isoprenoids, unresolved complex mixtures (UCM), volatile monoaromatic compounds--benzene, toluene, ethylbenzene and xylenes (BTEX), parent and alkylated homologues polycyclic aromatic hydrocarbons (PAH), and terpanes and steranes were characterized for determining correlation to the spilled oil and other known oil sources and environmental assessment. Some of the acute ecotoxicity data for water and sediment samples is also presented.     

Brazilian Oil Spills Chemical Characterization—Case Studies

In the last decade, PETROBRAS has experienced some significant oil spills cases and the PETROBRAS Research Center has played an important role in the company emergency response program by characterizing the spilled oil, monitoring the affected ecosystem, determining the fate of the oil in the environment, and, subsequently, helping the company in assessing the environmental damage. This paper presents the use of advanced chemical analytical techniques (GC/FID, P&T/GC/PID and GC/MS) in some Brazilian oil spill studies in order to determine fractions and individual petroleum hydrocarbons in different matrices such as water, groundwater, sediment, sand, fish and the spilled oil itself. The spill studies encompassed crude and fuel oil releases on land and coastal ecosystems, related to the incidents in Guanabara Bay (Rio de Janeiro), Barigui and Iguassu Rivers (Parana) and Sao Sebastiao Channel (Sao Paulo). Total petroleum hydrocarbons (TPH), n -alkanes, isoprenoids, unresolved complex mixtures (UCM), volatile monoaromatic compounds—benzene, toluene, ethylbenzene and xylenes (BTEX), parent and alkylated homologues polycyclic aromatic hydrocarbons (PAH), and terpanes and steranes were characterized for determining correlation to the spilled oil and other known oil sources and environmental assessment. Some of the acute ecotoxicity data for water and sediment samples is also presented.     

Solubility of toluene,benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.     

Multibiomarker approach in fish to assess the impact of pollution in a large Brazilian river, Paraiba do Sul

This article examines the advantages of the use of biomarkers as environmental indicators by applying it to Paraiba do Sul watershed, one of the most important Brazilian water bodies, which is in a critical environmental situation. We use a multibiomarker approach in fish as an integrated strategy to assess the impact of pollution. It comprehends a general biomarker of fish health, the condition factor (CF), and specific biomarkers of contaminant exposure such as metallothionein (MT), acetylcholinesterase (AChE) activity and biliary polycyclic aromatic hydrocarbons (PAH) metabolites. Our results revealed different effects in the fish from diverse locations with varying degrees of pollution. Furthermore, fish located just upstream of the water-treatment plant of the metropolitan area of Rio de Janeiro has shown to be affected by metals. This study indicates the usefulness of integrating a set of biomarkers to define the effects of anthropogenic inputs in aquatic bodies under complex polluted situations.     

Measurements of aromatic hydrocarbon ratios and NOx concentrations in the rural troposphere: Observation of air mass photochemical aging and NOx removal

Measurements of the aromatic hydrocarbons (benzene, toluene, ethylbenzene and ortho(o)-xylene) at Niwot Ridge, Colorado have shown distinct correlations between the ratios of the concentrations of these compounds and the degree of direct urban influence. The major atmospheric removal mechanism of aromatic hydrocarbons is reaction with the hydroxyl radical, OH. This allows the decrease in the ratios of aromatic hydrocarbon concentrations to be related to the transport time and average OH number density within an air mass, if assumptions are made concerning background sources of aromatic hydrocarbons. Measured ratios of aromatic compounds at this site, along with ratios reported for several cities in the western United States, and estimates of transport times from these cities were used to calculate temporally and spatially averaged OH number densities. Hydroxyl radical number density estimates using toluene-, ethylbenzene-, and o-xylene-to-benzene ratios, were 1.2 ± 0.6 × 10⁶, 1.0 ±0.8 × 10₆ and 0.48 ± 0.8 × 10⁶ molecules cm⁻³, respectively. Considering the uncertainties in the assumptions used in the above estimates, we obtain a diurnal-average upper limit of 2.4 × 10⁶ molecules cm⁻³. The correlations between measured ratios are found to yield slopes consistent with those predicted by experimental OH rate constants for benzene, toluene and ethylbenzene, and approximately a factor of two different in the case of benzene, toluene and o-xylene. The ratio of NO_x: benzene was found to yield no correlation with toluene: benzene ratio for periods of westerly flow, but was well correlated with toluene: benzene ratio during periods of direct urban impact on the site (upslope easterly winds). The correlation of these ratios in urban plume air masses was consistent with NO₂ + OH + M being the major daytime removal mechanism of NO_x in the summertime.     

Variation in PAH inputs and microbial community in surface sediments of Hamilton Harbour: implications to remediation and monitoring

Variations in concentrations of polycyclic aromatic hydrocarbons (PAHs) and microbial community indicators were investigated in representative highly contaminated and less contaminated surface sediment sites of Hamilton Harbour. Inputs of PAH to the upper 3cm of sediments up to four times the average upper sediment concentrations were observed. Associated PAH fingerprint profiles indicated that the source was consistent with the PAH source to the industrial region of the harbour. Increased PAH loadings were associated with decreased bacterial populations as indicated by phospholipid fatty acid (PLFA) concentrations. However, relatively minor impacts on overall community composition were indicated. Porewater methane concentrations and isotopic data indicated a difference in the occurrence of methane oxidation between the two sites. This study confirms temporally limited transport of contaminants from highly impacted regions as a vector for contaminants within the harbour and the impact on microbial carbon cycling and bed stability.     

Characteristics and diurnal variations of NMHCs at urban,suburban, and rural sites in the Pearl River Delta and a remote site in South China

The Pearl River Delta (PRD) is one of the most industrialized and urbanized regions in China. With rapid growth of the economy, it is suffering from deteriorating air quality. Non-methane hydrocarbons (NMHCs) were investigated at urban and suburban sites in Guangzhou (GZ), a rural site in PRD and a clean remote site in South China, in April 2005. Additional roadside samples in GZ and Qingxi (QX, a small industrial town in PRD), ambient air samples at the rooftop of a printing factory in QX and exhaust samples from liquefied petroleum gas (LPG)—fueled taxis in GZ were collected to help identify the source signatures of NMHCs. A large fraction of propane (47%) was found in exhaust samples from LPG-fueled taxis in GZ and extremely high levels of toluene (2.0–3.1 ppmv) were found at the rooftop of the printing factory in QX. Vehicular and industrial emissions were the main sources of NMHCs. The effect of vehicular emission on the ambient air varied among the three PRD sites. The impact of industrial emissions was widespread and they contributed greatly to the high levels of aromatic hydrocarbons, especially toluene, at the three PRD sites investigated. Leakage from vehicles fueled by LPG contributed mainly to the high levels of propane and n-butane at the urban GZ site. Ethane and ethyne from long-range transport and isoprene from local biogenic emission were the main contributors to the total hydrocarbons at the remote site. Diurnal variations of NMHCs showed that the contribution from vehicular emissions varied with traffic conditions and were more influenced by fresh emissions at the urban site and by aged air at the suburban and rural sites. Isoprene from biogenic emission contributed largely to the ozone formation potential (OFP) at the remote site. Ethene, toluene and m/p-xylene were the main contributors to the OFP at the three PRD sites.     

Effect of Methanol on Exhaust Composition of a Fuel Containing Toluene,n-Heptane,and Isooctane

This study describes the variations in the chemical composition of the exhaust from a single cylinder engine when up to 25% methanol is added to a fuel blend of toluene, isooctane, and n-heptane. Under fuel-rich conditions, and with increasing methanol concentration, it is observed that unburned fuel and benzene emissions increase, exhaust acetylene remains constant, and propylene, isobutylene, methane, ethylbenzene, and styrene concentrations decrease. As oxygen becomes more available, the effects of methanol are reduced, and at an equivalence ratio of 1.25—excess oxygen now is present—methanol no longer affects the concentration of exhaust hydrocarbons. These observations are explained by the reactions of formaldehyde—an incomplete combustion product of methanol— with alkyl radicals derived from the fuel. The photochemical reactivity of the exhaust is unchanged when up to 15% of methanol is present in the fuel at an equivalence ratio of 0.85, but increases at higher methanol contents because of the increase in unburned toluene in the exhaust.     

Aromatic hydrocarbons at urban,sub-urban,rural (8°52′N; 67°19′W) and remote sites in Venezuela

Using the novel on-line proton transfer reaction mass spectrometry (PTR-MS) technique, atmospheric concentrations of benzene, toluene, xylenes, and C₉-benzenes were measured in Caracas (urban), Altos de Pipe (sub-urban), Calabozo (rural) and Parupa (remote), during various campaigns in 1999 and 2000.Average daytime mixing ratios measured in Caracas are 1.1, 3.2, 3.7, and 2.7 nmol/mol for benzene, toluene, xylenes, and C₉-benzenes. At the sub-urban site, located only few km from Caracas, relatively low levels (∼20% of the levels measured in Caracas) of these aromatic hydrocarbons were observed.At the rural site during the dry season, higher concentrations of benzene (0.15 nmol/mol) were recorded, whereas those of toluene (0.08 nmol/mol) were lower during that time. The aromatic hydrocarbon ratios in the wet season (benzene: 0.08 nmol/mol; toluene: 0.09 nmol/mol) are consistent with an aged urban plume, whereas biomass burning emissions dominate during the dry season. From rural and urban [benzene]/[toluene] ratios a mean HO concentration of 2.6×10⁶ molecules/cm³ was estimated during the wet season. This value must be considered an overestimate because it does not account for background concentrations which are likely for benzene and toluene.At the remote “La Gran Sabana” region (Parupa) very low mixing ratios (0.031 and 0.015 nmol/mol for benzene and toluene) are showing the pristine region to be unaffected by local sources. From the [benzene]/[toluene] ratio we deduced, that “urban” air arriving from the coastline (350 km) is likely mixed with air containing some background of benzene and toluene.Urban emissions (automobiles) should be the major source of aromatic compounds, however, during the dry season biomass burning seems to make an important contribution.     

Near-road air pollution impacts of goods movement in communities adjacent to the Ports of Los Angeles and Long Beach

A mobile platform was outfitted with real-time instruments to spatially characterize pollution concentrations in communities adjacent to the Ports of Los Angeles and Long Beach, communities heavily impacted by emissions related to dieselized goods movement, with the highest localized air pollution impacts due to heavy-duty diesel trucks (HDDT). Measurements were conducted in the winter and summer of 2007 on fixed routes driven both morning and afternoon. Diesel-related pollutant concentrations such as black carbon, nitric oxide, ultrafine particles, and particle-bound polycyclic aromatic hydrocarbons were frequently elevated two to five times within 150 m downwind of freeways (compared to more than 150 m) and up to two times within 150 m downwind of arterial roads with significant amounts of diesel traffic. While wind direction was the dominant factor associated with downwind impacts, steady and consistent wind direction was not required to produce; high impacts were observed when a given area was downwind of a major roadway for any significant fraction of time. This suggests elevated pollution impacts downwind of freeways and of busy arterials are continuously occurring on one side of the road or the other, depending on wind direction. The diesel truck traffic in the area studied was high, with more than 2000 trucks per peak hour on the freeway and two- to six-hundred trucks per hour on the arterial roads studied. These results suggest that similarly-frequent impacts occur throughout urban areas in rough proportion to diesel truck traffic fractions. Thus, persons living or working near and downwind of busy roadways can have several-fold higher exposures to diesel vehicle-related pollution than would be predicted by ambient measurements in non-impacted locations.     

Fast and quantitative measurement of benzene,toluene and C2-benzenes in automotive exhaust during transient engine operation with and without catalytic exhaust gas treatment

Time-Resolved Chemical Ionization Mass Spectrometry (CIMS) has been used to investigate the emission profiles of benzene, toluene and the C₂-benzenes (xylenes and ethyl benzene) in automotive exhaust during transient engine operation. On-line emission measurements with a frequency of 1–5 Hz clearly identified the critical driving conditions that are mainly responsible for the overall aromatic hydrocarbon emissions. The passenger car, equipped with a catalytic converter showed significant BTXE-emissions only in the first part of the New European Driving Cycle (NEDC) due to sub-optimal catalyst temperature. On the same car without a catalytic converter, emissions of aromatic hydrocarbons were detected over the entire test run and the benzene–toluene mixing ratios of the exhaust gas were rather constant. With catalytic exhaust gas treatment the observed benzene–toluene mixing ratios varied to a greater extent reflecting predominantly different catalytic converter conditions. The average molar ratio of benzene over toluene rose from 0.33 to 0.53 upon exhaust gas treatment. With catalytic converter the emissions during extra urban (EUDC) driving repeatedly showed benzene–toluene mixing ratios >1 and an average molar benzene/toluene ratio of 0.74 was detected during the EUDC part of the driving cycle. Whereas the total hydrocarbon (T.HC) emissions were decreased by 83% upon exhaust gas treatment the overall reduction of the benzene emissions was only 70%.     

A comparative study on the recovery of polycyclic aromatic hydrocarbons from fly ash and lignite coal

The recovery of polycyclic aromatic hydrocarbons (PAHs) from lignite coal burnt in Greek power stations and the fly ash produced is examined comparatively using Soxhlet, ultrasonic and accelerated solvent extraction procedures with various organic solvents. Soxhlet using toluene/methanol mixture and accelerated solvent extraction/toluene were found to be the most efficient methods for fly ash PAHs, yielding average recoveries of about 80%. The accelerated solvent extraction/toluene procedure was superior for lignite PAHs, yielding 96% average recovery, whereas ultrasonic and Soxhlet extraction yielded relatively lower recoveries (75% and 67%, respectively).     

MTBE and aromatic hydrocarbons in North Carolina stormwater runoff

A total of 249 stormwater samples were collected from 46 different sampling locations in North Carolina over an approximate 1-year period and analyzed to identify land use types where fuel oxygenates and aromatic hydrocarbons may be present in higher concentrations and at greater frequency. Samples were analyzed by gas chromatography-mass spectrometry in ion selective mode to achieve a quantitation limit of 0.05 microg/l. m-,p-Xylene and toluene were detected in over half of all samples analyzed, followed by MTBE: o-xylene: 1,3,5-trimethylbenzene: ethylbenzene; and 1,2,4-trimethylbenzene. Benzene, DIPE, TAME and 1,2,3-trimethylbenzene were detected in < 10% of the samples analyzed. Median contaminant concentrations (when detected) varied from 0.07 microg/l for ethylbenzene to 0.11 microg/l for toluene. All of the locations with significantly higher contaminant concentrations were associated with direct runoff from a gas station or discharge of contaminated groundwater from a former leaking underground storage tank. For all of the aromatic hydrocarbons, the maximum observed contaminant concentrations were over an order of magnitude lower than current drinking water standards.     

A strategy for aromatic hydrocarbon bioremediation under anaerobic conditions and the impacts of ethanol: a microcosm study

Increased use of ethanol-blended gasoline (gasohol) and its potential release into the subsurface have spurred interest in studying the biodegradation of and interactions between ethanol and gasoline components such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) in groundwater plumes. The preferred substrate status and the high biological oxygen demand (BOD) posed by ethanol and its biodegradation products suggests that anaerobic electron acceptors (EAs) will be required to support in situ bioremediation of BTEX. To develop a strategy for aromatic hydrocarbon bioremediation and to understand the impacts of ethanol on BTEX biodegradation under strictly anaerobic conditions, a microcosm experiment was conducted using pristine aquifer sand and groundwater obtained from Canadian Forces Base Borden, Canada. The initial electron accepter pool included nitrate, sulfate and/or ferric iron. The microcosms typically contained 400 g of sediment, 600 approximately 800 ml of groundwater, and with differing EAs added, and were run under anaerobic conditions. Ethanol was added to some at concentrations of 500 and 5000 mg/L. Trends for biodegradation of aromatic hydrocarbons for the Borden aquifer material were first developed in the absence of ethanol, The results showed that indigenous microorganisms could degrade all aromatic hydrocarbons (BTEX and trimethylbenzene isomers-TMB) under nitrate- and ferric iron-combined conditions, but not under sulfate-reducing conditions. Toluene, ethylbenzene and m/p-xylene were biodegraded under denitrifying conditions. However, the persistence of benzene indicated that enhancing denitrification alone was insufficient. Both benzene and o-xylene biodegraded significantly under iron-reducing conditions, but only after denitrification had removed other aromatics. For the trimethylbenzene isomers, 1,3,5-TMB biodegradation was found under denitrifying and then iron-reducing conditions. Biodegradation of 1,2,3-TMB or 1,2,4-TMB was slower under iron-reducing conditions. This study suggests that addition of excess ferric iron combined with limited nitrate has promise for in situ bioremediation of BTEX and TMB in the Borden aquifer and possibly for other sites contaminated by hydrocarbons. This study is the first to report 1,2,3-TMB biodegradation under strictly anaerobic condition. With the addition of 500 mg/L ethanol but without EA addition, ethanol and its main intermediate, acetate, were quickly biodegraded within 41 d with methane as a major product. Ethanol initially present at 5000 mg/L without EA addition declined slowly with the persistence of unidentified volatile fatty acids, likely propionate and butyrate, but less methane. In contrast, all ethanol disappeared with repeated additions of either nitrate or ferric iron, but acetate and unidentified intermediates persisted under iron-enhanced conditions. With the addition of 500 mg/L ethanol and nitrate, only minor toluene biodegradation was observed under denitrifying conditions and only after ethanol and acetate were utilized. The higher ethanol concentration (5000 mg/L) essentially shut down BTEX biodegradation likely due to high EA demand provided by ethanol and its intermediates. The negative findings for anaerobic BTEX biodegradation in the presence of ethanol and/or its biodegradation products are in contrast to recent research reported by Da Silva et al. [Da Silva, M.L.B., Ruiz-Aguilar, G.M.L., Alvarez, P.J.J., 2005. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate. Biodegradation. 16, 105-114]. Our results suggest that the apparent conservation of high residual labile carbon as biodegradation products such as acetate makes natural attenuation of aromatics less effective, and makes subsequent addition of EAs to promote in situ BTEX biodegradation problematic.     

Sediment-associated aliphatic and aromatic hydrocarbons in coastal British Columbia, Canada: concentrations, composition, and associated risks to protected sea otters

Sediment-associated hydrocarbons can pose a risk to wildlife that rely on benthic marine food webs. We measured hydrocarbons in sediments from the habitat of protected sea otters in coastal British Columbia, Canada. Alkane concentrations were dominated by higher odd-chain n-alkanes at all sites, indicating terrestrial plant inputs. While remote sites were dominated by petrogenic polycyclic aromatic hydrocarbons (PAHs), small harbour sites within sea otter habitat and sites from an urban reference area reflected weathered petroleum and biomass and fossil fuel combustion. The partitioning of hydrocarbons between sediments and adjacent food webs provides an important exposure route for sea otters, as they consume ∼25% of their body weight per day in benthic invertebrates. Thus, exceedences of PAH sediment quality guidelines designed to protect aquatic biota at 20% of the sites in sea otter habitat suggest that sea otters are vulnerable to hydrocarbon contamination even in the absence of catastrophic oil spills.     

Polycyclic aromatic hydrocarbons in crude oil-contaminated soil: A two-step method for the isolation and characterization of PAHs

A two-step analytical method is developed for the isolation and characterization of polycyclic aromatic hydrocarbons (PAHs) in crude oil contaminated soil. In the first step, those crude oil components were isolated which are easily mobilized with water from the contaminated soil (determination of groundwater pollution potential). In the second step, the fraction containing the remaining crude oil compounds was extracted using toluene. After the cleanup of the fractions, both fractions were analyzed using high-performance liquid chromatography (HPLC). The HPLC of the toluene extracted fraction shows that along with the sixteen priority pollutants from the US-EPA list, many other polycyclic aromatic hydrocarbons (PAHs) are present as well. It is evident from the chromatograms that a significant amount of PAHs are present as is also the case in the fractions eluted by water. The described method allows the determination of total organic pollutants from crude oil, some of them being potential groundwater contaminants. The major part of the total pollutants could not be mobilized by water and therefore remains in the soil, which was extracted in the second step.     

The effect of structural compositions on the biosorption of phenanthrene and pyrene by tea leaf residue fractions as model biosorbents

To enhance the removal efficiency of polycyclic aromatic hydrocarbons (PAHs) by natural biosorbent, sorption of phenanthrene and pyrene onto raw and modified tea leaves as a model biomass were investigated. Tea leaves were treated using Soxhlet extraction, saponification, and acid hydrolysis to yield six fractions. The structures of tea leaf fractions were characterized by elemental analysis, Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM). The amorphous cellulose components regulated the sorption kinetics, capacity, and mechanism of biomass fractions. The adsorption kinetics fit well to pseudo-second-order model and isotherms followed the Freundlich equation. By the consumption of the amorphous cellulose under acid hydrolysis, both the aliphatic moieties and aromatic domains contributed to total sorption, thus sorption capacities of the de-sugared fractions were dramatically increased (5–20-fold for phenanthrene and 8–36-fold for pyrene). All de-sugared fractions exhibited non-linear sorption due to strong specific interaction between PAHs and exposed aromatic domains of biosorbent, while presenting a relative slow rate because of the condensed domain in de-sugared samples. The availability of strong sorption phases (aromatic domains) in the biomass fractions were controlled by polar polysaccharide components, which were supported by the FTIR, CHN, and SEM data.     

Temporal trends of hydrocarbons in sediment cores from the Pearl River Estuary and the northern South China Sea

Concentrations and fluxes of unresolved complex mixture of hydrocarbons (UCM) and polycyclic aromatic hydrocarbons (PAHs) were analyzed for two ²¹⁰Pb dated sediment cores from the Pearl River Estuary (PRE) and the adjacent northern South China Sea (NSCS). Compound-specific stable carbon isotopic compositions of individual n-alkanes were also measured for identification of the hydrocarbon sources. The historical records of PAHs in the NSCS reflected the economic development in the Pearl River Delta during the 20th century. PAHs in the NSCS predominantly derive from combustion of coal and biomass, whereas PAHs in the PRE are a mixture of petrogenic and pyrogenic in origins. The isotopic profiles reveal that the petrogenic hydrocarbons in the PRE originate predominantly from local spillage/leakage of lube oil and crude oils. The accumulation rates of pyrogenic PAHs have significantly increased, whereas UCM accumulation has slightly declined in the NSCS in the recent three decades.