Benzene polycarboxylic acids as molecular markers of black carbon: Progresses and challenges.

Black carbon (BC) is generated as a result of the pyrolysis of biomass and fossil fuels. Different approaches have been taken to analyse BC in the environment, including thermal, optical and chemical methods. The chemical approach which uses benzene polycarboxylic acids (BPCAs) as molecular markers of BC has gained popularity within the scientific community recently. These pyrogenic molecular markers can be used to reconstruct ancient fire history and human presence. Here we review the development of the BPCA protocols for the analysis of BC and the previous studies that have used these methods. Additionally, this review explores the biogeochemical factors that influence the content and composition of BPCAs, which in turn affect the sources attributed to BC. These factors include the generation temperature of char, photodegradation, biodegradation and the interference of non-pyrogenic organic matter (OM) in BPCA-BC analysis. Different combustion temperatures can yield charred BC with varying degrees of aromatic condensation throughout the BC continuum, while aged soot-BC undergoes photochemical degradation, causing the loss of its original condensed aromatic structure. Photodegradation reduces the degree of BC condensation by preferentially breaking down the most condensed forms, whereas biodegradation primarily mineralizes the smaller and more biolabile BC. Non-pyrogenic sources, such as humic acids (HAs), have been found to contribute up to 25% of BPCA-BC in soil, and their presence can lead to overestimations of BC. Future research should focus on calibrating contemporary BPCA protocols using known reference materials and investigating the role of non-pyrogenic OM in BPCA-BC analysis.

Characteristics of dissolved black carbon in riverine surface microlayer.

Black carbon (BC) is produced by the incomplete combustion of biomass and fossil fuels. The dissolved form of BC (DBC), which is transported through rivers into the oceans, is of great significance for the carbon cycling on the planet due to its refractory features. However, the characteristics and sources of DBC in riverine water are poorly constrained. Here, we analyzed DBC contents and stable carbon isotope (δ13C) signatures in surface microlayer (SML) from the upper, middle and lower reaches of Pearl River (PR) in the first study of its kind. The DBC contents (100.9 to 166.6 µg L-1) in SML were lower than the global average for riverine water following a trend of upper > middle > lower reaches in PR. The molecular markers of DBC (BPCAs) and their δ13C values showed no statistical differences between the sampling sites (p > 0.05), suggesting biomass burning as the dominant source.

Monitoring of linear alkyl benzenes (LABs) in riverine and estuarine sediments in Malaysia.

The aim of this a pioneering research is to investigate linear alkylbenzenes (LABs) as biomarkers of sewage pollution in sediments collected from four rivers and estuaries of the south and east of Peninsular Malaysia. The sediment samples went through soxhlet extraction, two-step column chromatography purification, fractionation and gas chromatography-mass spectrometry (GC-MS) analysis. Principal component analysis (PCA) with multivariate linear regression (MLR) was used as well for source apportionment of LABs. The results of this study showed that total LAB concentration was 36-1196 ng g-1dw. The internal to external isomer ratios (I/E ratio) of LABs were from 0.56 to 3.12 indicated release of raw sewage and primary and secondary effluents into the environment of south and east of Peninsular Malaysia. Our research supported that continuous monitoring of sewage pollution to limit the environmental pollution in riverine and estuarine ecosystem.

Distribution of black carbon and PAHs in sediments of Peninsular Malaysia.

Concentrations, sources and interactions between black carbon (BC) and polycyclic aromatic hydrocarbons (PAHs) were investigated in 42 sediment samples collected from riverine, coastal and shelf areas in Peninsular Malaysia. The concentrations of BC measured by benzene polycarboxylic acid (BPCA) method and PAHs showed broad spatial variations between the relatively pristine environment of the East coast and developed environment of the West and South coast ranging from 0.02 to 0.36% dw and 57.7 ng g-1 dw to 19,300 ng g-1 dw, respectively. Among diagnostic ratios of PAHs, the ratios of Ant/(Ant+Phe) and LMW/HMW drew the clearest distinctions between the East coast versus the West and South coast sediments indicating the predominance of petrogenic sources in the former versus pyrogenic sources in the latter. PAHs significantly correlated with BC and total organic carbon (TOC) in the sediments (p < 0.05) having similar correlation coefficients. BC accounted for 6.06 to 30.6% of TOC in sediments.

Examination of barnacles' potential to be used as bioindicators of persistent organic pollutants in coastal ecosystem: A Malaysia case study.

Barnacles are ubiquitous in coastal ecosystems of different geographical regions worldwide. This is the first study attempting to assess the suitability of barnacles as bioindicators of persistent organic pollutants (POPs) in coastal environments. Barnacles were collected from the coasts around Peninsular Malaysia and analyzed for POPs including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs). Among POPs, PCBs showed the highest concentrations with elevated contributions of CB28 and CB153. As for PBDEs, BDE47 was the most frequently detected congener, while BDE209 was detected in barnacles from two stations in Port Klang and the levels reached up to >70% of total PBDE concentrations. Concentrations of OCPs detected in barnacles were in the order of CHLs > DDTs > HCHs > HCB and 4,4'-DDE and cis- and trans-chlordane were the predominant OCP compounds. A comparison with previous studies in Malaysia showed consistent levels of POPs. Green mussels collected from selected barnacles' habitats, for the sake of a comparison, showed almost similar profiles but lower concentrations of POPs. The spatial distribution of POPs observed in barnacles and comparison of POP levels and profiles with mussels indicated that barnacles can be useful bioindicators for monitoring POPs contamination in the coastal ecosystems.

Correction to: Use of sterols and linear alkylbenzenes as molecular markers of sewage pollution in Southeast Asia.

The original publication of this paper contains a mistake. The correct image of figure 2 is shown in this paper.

Use of sterols and linear alkylbenzenes as molecular markers of sewage pollution in Southeast Asia.

Southeast Asia has undergone rapid developments in terms of urbanization, economic and population growth. The progress in sewerage treatment infrastructure has not kept pace with such developments. The inadequacy and inefficiency of sewerage systems has prompted the release of untreated sewage into the aquatic environment of Southeast Asia causing many waterborne illnesses since surface water is utilized for recreational, agricultural and aquaculture purposes and, above all, as a source of water intake in Southeast Asia. This paper will review the current data on molecular markers of sewage pollution including sterols and linear alkylbenzenes (LABs) in Southeast Asian aquatic environment to clarify the state of sewage pollution and the competence of sewage treatment plants (STPs) in this area. Despite the importance of sewage pollution research in the region, the number of studies using molecular markers to trace the sources of sewage pollution is limited. So far, indicators of sewage pollution have been investigated in aquatic environments of Indonesia, Vietnam, Malaysia, the Philippines, Thailand, Cambodia and Brunei among Southeast Asian countries. The concentrations and diagnostic ratios of faecal sterols and LABs show the release of untreated and primary treated urban waste into water bodies of these countries. Further studies are required to fill the data gaps in Southeast Asia and come to a better understanding of the trends of sewage pollution in this part of the world. Graphical abstract.

Seasonal variability of anthropogenic indices of PAHs in sediment from the Kuala Selangor River, west coast Peninsular Malaysia.

Rapid increase in industrialization and urbanization in the west coast of Peninsular Malaysia has led to the intense release of petroleum and products of petroleum into the environment. Surface sediment samples were collected from the Selangor River in the west coast of Peninsular Malaysia during four climatic seasons and analyzed for PAHs and biomarkers (hopanes). Sediments were soxhlet extracted and further purified and fractionated through first and second step column chromatography. A gas chromatography-mass spectrometry (GC-MS) was used for analysis of PAHs and hopanes fractions. The average concentrations of total PAHs ranged from 219.7 to 672.3 ng g-1 dw. The highest concentrations of PAHs were detected at 964.7 ng g-1 dw in station S5 in the mouth of the Selangor River during the wet inter-monsoonal season. Both pyrogenic and petrogenic PAHs were detected in the sediments with a predominance of the former. The composition of hopanes was homogeneous showing that petroleum hydrocarbons share an identical source in the study area. Diagnostic ratios of hopanes indicated that some of the sediment samples carry the crankcase oil signature.

Aliphatic hydrocarbons and triterpane biomarkers in mangrove oyster (Crassostrea belcheri) from the west coast of Peninsular Malaysia.

The Straits of Malacca is one of the world's busiest shipping routes where frequent oil spills occur. Rapid development in the west coast of Peninsular Malaysia is the other major source of petroleum pollution in this narrow waterway. In order to identify occurrence and origin of hydrocarbons in the Straits, mangrove oysters (Crassostrea belcheri) were collected from five sampling locations and analysed for n-alkanes and biomarkers. Soxhlet apparatus and two step column chromatography were used for extraction, purification and fractionation of the oysters. Petroleum origin n-alkanes were detected in majority of the sampling locations which is indicative of anthropogenic activities in this region. Using source and maturity diagnostic ratios for hopanes revealed used crankcase oil as the main source of petroleum hydrocarbons in oysters from all sampling locations except for the Pulau Merambong where signature of South East Asia crude oil (SEACO) was detected.

Evaluation of distribution and sources of sewage molecular marker (LABs) in selected rivers and estuaries of Peninsular Malaysia.

This is the first extensive report on linear alkylbenzenes (LABs) as sewage molecular markers in surface sediments collected from the Perlis, Kedah, Merbok, Prai, and Perak Rivers and Estuaries in the west of Peninsular Malaysia. Sediment samples were extracted, fractionated, and analyzed using gas chromatography mass spectrometry (GC-MS). The concentrations of total LABs ranged from 68 to 154 (Perlis River), 103 to 314 (Kedah River), 242 to 1062 (Merbok River), 1985 to 2910 (Prai River), and 217 to 329 ng g(-1) (Perak River) dry weight (dw). The highest levels of LABs were found at PI3 (Prai Estuary) due to the rapid industrialization and population growth in this region, while the lowest concentrations of LABs were found at PS1 (upstream of Perlis River). The LABs ratio of internal to external isomers (I/E) in this study ranged from 0.56 at KH1 (upstream of Kedah River) to 1.35 at MK3 (Merbok Estuary) indicating that the rivers receive raw sewage and primary treatment effluents in the study area. In general, the results of this paper highlighted the necessity of continuation of water treatment system improvement in Malaysia.

Anthropogenic waste indicators (AWIs), particularly PAHs and LABs, in Malaysian sediments: Application of aquatic environment for identifying anthropogenic pollution.

Polycyclic aromatic hydrocarbons (PAHs) and linear alkylbenzenes (LABs) were used as anthropogenic markers of organic chemical pollution of sediments in the Selangor River, Peninsular Malaysia. This study was conducted on sediment samples from the beginning of the estuary to the upstream river during dry and rainy seasons. The concentrations of Æ©PAHs and Æ©LABs ranged from 203 to 964 and from 23 to 113 ng g(-1) dry weight (dw), respectively. In particular, the Selangor River was found to have higher sedimentary levels of PAHs and LABs during the wet season than in the dry season, which was primarily associated with the intensity of domestic wastewater discharge and high amounts of urban runoff washing the pollutants from the surrounding area. The concentrations of the toxic contaminants were determined according to the Sediment Quality Guidelines (SQGs). The PAH levels in the Selangor River did not exceed the SQGs, for example, the effects range low (ERL) value, indicating that they cannot exert adverse biological effects.

Baseline distribution and sources of linear alkyl benzenes (LABs) in surface sediments from Brunei Bay, Brunei.

Sewage pollution is one of major concerns of coastal and shoreline settlements in Southeast Asia, especially Brunei. The distribution and sources of LABs as sewage molecular markers were evaluated in surface sediments collected from Brunei Bay. The samples were extracted, fractionated and analyzed using gas chromatography- mass spectrometry (GC-MS). LABs concentrations ranged from 7.1 to 41.3 ng g(-1) dry weight (dw) in surficial sediments from Brunei Bay. The study results showed LABs concentrations variably due to the LABs intensity and anthropogenic influence along Brunei Bay in recent years. The ratio of Internal to External isomers (I/E ratio) of LABs in sediment samples from Brunei Bay ranged from 0.56 to 2.17 along Brunei Bay stations, indicating that the study areas were receiving primary and secondary effluents. This is the first study carried out to assess the distribution and sources of LABs in surface sediments from Brunei Bay, Brunei.

Forensic investigation of aliphatic hydrocarbons in the sediments from selected mangrove ecosystems in the west coast of Peninsular Malaysia.

Peninsular Malaysia has gone through fast development during recent decades resulting in the release of large amounts of petroleum and its products into the environment. Aliphatic hydrocarbons are one of the major components of petroleum. Surface sediment samples were collected from five rivers along the west coast of Peninsular Malaysia and analyzed for aliphatic hydrocarbons. The total concentrations of C10 to C36 n-alkanes ranged from 27,945 to 254,463ng·g(-1)dry weight (dw). Evaluation of various n-alkane indices such as carbon preference index (CPI; 0.35 to 3.10) and average chain length (ACL; 26.74 to 29.23) of C25 to C33 n-alkanes indicated a predominance of petrogenic source n-alkanes in the lower parts of the Rivers, while biogenic origin n-alkanes from vascular plants are more predominant in the upper parts, especially in less polluted areas. Petrogenic sources of n-alkanes are predominantly heavy and degraded oil versus fresh oil inputs.

Baseline distributions and sources of Polycyclic Aromatic Hydrocarbons (PAHs) in the surface sediments from the Prai and Malacca Rivers, Peninsular Malaysia.

In this study, the surface sediments of the Malacca and Prai Rivers were analyzed to identify the distributions, and sources of Polycyclic Aromatic Hydrocarbons (PAHs). The total PAH concentrations varied from 716 to 1210 and 1102 to 7938 ng g(-1)dw in the sediments of the Malacca and Prai Rivers, respectively. The PAH concentrations can be classified as moderate and high level of pollution in the sediments of the Malacca and Prai Rivers, respectively. The comparison of PAHs with the Sediment Quality Guidelines (SQGs) indicates that the PAHs in the sediments of the Malacca and Prai Rivers may have the potential to cause adverse toxicity effects on the sampled ecosystems. The diagnostic ratios of individual PAHs indicate both petrogenic- and pyrogenic-origin PAHs with dominance of pyrogenic source in both rivers. These findings demonstrate that the environmental regulations in Malaysia have effectively reduced the input of petrogenic petroleum hydrocarbons into rivers.