Nineteen pairs of gaseous and surface seawater samples were collected along the cruise from Malaysia to the south of Bay of Bengal passing by Sri Lanka between April 12 and May 4, 2011 on the Chinese research vessel Shiyan I to investigate the latest OCP pollution status over the equatorial Indian Ocean. Significant decrease of α-HCH and γ-HCH was found in the air and dissolved water phase owing to global restriction for decades. Substantially high levels of p,p'-DDT, o,p'-DDT, trans-chlordane (TC), and cis-chlordane (CC) were observed in the water samples collected near Sri Lanka, indicating fresh continental riverine input of these compounds. Fugacity fractions suggest equilibrium of α-HCH at most sampling sites, while net volatilization for DDT isomers, TC and CC in most cases. Enantiomer fractions (EFs) of α-HCH and o,p'-DDT in the air and water samples were determined to trace the source of these compounds in the air. Racemic or close to racemic composition was found for atmospheric α-HCH and o,p'-DDT, while significant depletion of (+) enantiomer was found in the water phase, especially for o,p'-DDT (EFs = 0.310 ± 0.178). 24% of α-HCH in the lower air over the open sea of the equatorial Indian Ocean is estimated to be volatilized from local seawater, indicating that long-range transport is the main source.
While the ecological impact of anthropogenically introduced exotic species is considered a major threat for biodiversity and ecosystems functioning, it is generally not accounted for in the environmental life cycle assessment (LCA) of products. In this article, we propose a framework that includes exotic species introduction in an LCA context. We derived characterization factors for exotic fish species introduction related to the transport of goods across the Rhine-Main-Danube canal. These characterization factors are expressed as the potentially disappeared fraction (PDF) of native freshwater fish species in the rivers Rhine and Danube integrated over space and time per amount of goods transported (PDF·m(3)·yr·kg(-1)). Furthermore, we quantified the relative importance of exotic fish species introduction compared to other anthropogenic stressors in the freshwater environment (i.e., eutrophication, ecotoxicity, greenhouse gases, and water consumption) for transport of goods through the Rhine-Main-Danube waterway. We found that the introduction of exotic fish species contributed to 70-85% of the total freshwater ecosystem impact, depending on the distance that goods were transported. Our analysis showed that it is relevant and feasible to include the introduction of exotic species in an LCA framework. The proposed framework can be further extended by including the impacts of other exotic species groups, types of water bodies and pathways for introduction.
The objective of this research was to investigate the relationship between lung cancer mortality rates, carcinogenic polycyclic aromatic hydrocarbon (PAH) emissions, and smoking on a global scale, as well as for different socioeconomic country groups. The estimated lung cancer deaths per 100,000 people (ED100000) and age standardized lung cancer death rate per 100,000 people (ASDR100000) in 2004 were regressed on PAH emissions in benzo[a]pyrene equivalence (BaPeq), smoking prevalence, cigarette price, gross domestic product per capita, percentage of people with diabetes, and average body mass index using simple and multiple linear regression for 136 countries. Using stepwise multiple linear regression, a statistically significant positive linear relationship was found between loge(ED100000) and loge(BaPeq) emissions for high (p-value <0.01) and for the combination of upper-middle and high (p-value <0.05) socioeconomic country groups. A similar relationship was found between loge(ASDR100000) and loge(BaPeq) emissions for the combination of upper-middle and high (p-value <0.01) socioeconomic country groups. Conversely, for loge(ED100000) and loge(ASDR100000), smoking prevalence was the only significant independent variable in the low socioeconomic country group (p-value <0.001). These results suggest that reducing BaPeq emissions in the U.S., Canada, Australia, France, Germany, Brazil, South Africa, Poland, Mexico, and Malaysia could reduce ED100000, while reducing smoking prevalence in Democratic People's Republic of Korea, Nepal, Mongolia, Cambodia, and Bangladesh could significantly reduce the ED100000 and ASDR100000.
Concentrations of 12 hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) were determined in 306 urine samples collected from seven Asian countries (China, India, Japan, Korea, Kuwait, Malaysia, and Vietnam) by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The total concentrations of OH-PAHs found in the seven Asian countries were in the following increasing order: Malaysia (median: 2260 pg/mL) < Japan (4030 pg/mL) < China (5770 pg/mL) < India (6750 pg/mL) < Vietnam (8560 pg/mL) < Korea (9340 pg/mL) < Kuwait (10170 pg/mL). The measured urinary concentrations of 1-hydroxypyrene (1-PYR) in samples from Malaysia, Korea, and Japan (∼ 100 pg/mL) were similar to those reported for North America and Western Europe. The concentrations of 1-PYR in urine samples from China, India, and Vietnam were 4-10 times higher than those reported for other countries, thus far. Among the 12 OH-PAH compounds analyzed, hydroxynaphthalene (NAP: sum of 1-hydroxynaphthalene and 2-hydroxynaphthalene) was the dominant compound (accounting for 60-90% of total OH-PAHs), followed by hydroxyphenanthrene (PHEN: sum of 2-hydroxyphenanthrene, 3-hydroxyphenanthrene, 4-hydroxyphenanthrene, and 9-hydroxyphenanthrene [3-16%]), 2-hydroxyfluorene (3-20%), and 1-PYR (2-8%). The total daily intakes (DIs) of PAHs were estimated based on the urinary concentrations of their metabolites. The DIs of naphthalene were found to be higher for populations in Korea, Kuwait, and Vietnam (> 10 μg/day) than those of the other countries studied (∼ 5 μg/day). The DIs of phenanthrene and pyrene (> 10 μg/day) in the populations of China, India, and Vietnam were higher than those estimated for the populations in the other countries studied (∼ 5 μg/day).
As concern regarding the toxic effects of bisphenol A (BPA) grows, BPA in many consumer products is gradually being replaced with compounds such as bisphenol S (BPS). Nevertheless, data on the occurrence of BPS in human specimens are limited. In this study, 315 urine samples, collected from the general populations in the United States, China, India, Japan, Korea, Kuwait, Malaysia, and Vietnam, were analyzed for the presence of total BPS (free plus conjugated) concentrations by high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). BPS was detected in 81% of the urine samples analyzed at concentrations ranging from below the limit of quantitation (LOQ; 0.02 ng/mL) to 21 ng/mL (geometric mean: 0.168 ng/mL). The urinary BPS concentration varied among countries, and the highest geometric mean concentration [1.18 ng/mLor 0.933 μg/g creatinine (Cre)] of BPS was found in urine samples from Japan, followed by the United States (0.299 ng/mL, 0.304 μg/g Cre), China (0.226 ng/mL, 0.223 μg/g Cre), Kuwait (0.172 ng/mL, 0.126 μg/g Cre), and Vietnam (0.160 ng/mL, 0.148 μg/g Cre). Median concentrations of BPS in urine samples from the Asian countries were 1 order of magnitude lower than the median concentrations reported earlier for BPA in the same set of samples, with the exception of samples from Japan. There were no significant differences in BPS concentrations between genders (male versus female), or among age groups (categorized as ≤ 19, 20-29, 30-39, 40-49, and ≥ 50 years), or races (Caucasian versus Asian). The daily intake (EDI) of BPS was estimated on the basis of urinary concentrations using a simple pharmacokinetic approach. The median EDI values of BPS in Japan, China, United States, Kuwait, Vietnam, Malaysia, India, and Korea were 1.67, 0.339, 0.316, 0.292, 0.217, 0.122, 0.084, and 0.023 μg/person, respectively. This is the first study to report the occurrence of BPS in human urine.
The problems of global warming and the unstable price of petroleum oils have led to a race to develop environmentally friendly biofuels, such as palm oil or ethanol derived from corn and sugar cane. Biofuels are a potential replacement for fossil fuel, since they are renewable and environmentally friendly. This paper evaluates the combustion performance and emission characteristics of Refined, Bleached, and Deodorized Palm Oil (RBDPO)/diesel blends B5, B10, B15, B20, and B25 by volume, using an industrial oil burner with and without secondary air. Wall temperature profiles along the combustion chamber axis were measured using a series of thermocouples fitted axially on the combustion chamber wall, and emissions released were measured using a gas analyzer. The results show that RBDPO blend B25 produced the maximum emission reduction of 56.9% of CO, 74.7% of NOx, 68.5% of SO(2), and 77.5% of UHC compared to petroleum diesel, while air staging (secondary air) in most cases reduces the emissions further. However, increasing concentrations of RBDPO in the blends also reduced the energy released from the combustion. The maximum wall temperature reduction was 62.7% for B25 at the exit of the combustion chamber.
Bisphenol A (BPA) is an industrial chemical used in the manufacture of polycarbonate plastics and epoxy resins. Due to the potential of this compound to disrupt normal endocrinal functions, concerns over human exposure to BPA have been raised. Although several studies have reported human exposure to BPA in Western nations, little is known about exposure in Asian countries. In this study, we determined total urinary BPA concentrations (free plus conjugated) in 296 urine samples (male/female: 153/143) collected from the general population in seven Asian countries, China, India, Japan, Korea, Kuwait, Malaysia, and Vietnam, using high-performance liquid chromatography (HPLC) tandem mass spectrometry (MS/MS). On the basis of urinary BPA concentrations, we estimated the total daily intake. The results indicated that BPA was detected in 94.3% of the samples analyzed, at concentrations ranging from <0.1 to 30.1 ng/mL. The geometric mean concentration of BPA for the entire sample set from seven countries was 1.20 ng/mL. The highest concentration of BPA was found in samples from Kuwait (median: 3.05 ng/mL, 2.45 μg/g creatinine), followed by Korea (2.17 ng/mL, 2.40 μg/g), India (1.71 ng/mL, 2.09 μg/g), Vietnam (1.18 ng/mL, 1.15 μg/g), China (1.10 ng/mL, 1.38 μg/g), Malaysia (1.06 ng/mL, 2.31 μg/g), and Japan (0.95 ng/mL, 0.58 μg/g). Among the five age groups studied (≤ 19, 20-29, 30-39, 40-49, and ≥ 50 years), the highest median concentration of BPA was found in urine samples from the age group of ≤ 19 years. There was no significant difference in BPA concentrations between genders (male and female) or domicile of residence (rural and urban). The estimated median daily intakes of BPA for the populations in Kuwait, Korea, India, China, Vietnam, Malaysia, and Japan were 5.19, 3.69, 2.90, 2.13, 2.01, 1.80, and 1.61 μg/day, respectively. The estimated daily intake of BPA in the seven Asian countries was significantly lower than the tolerable daily intake recommended by the U.S. Environmental Protection Agency. This is the first study to document the occurrence of and human exposure to BPA in several Asian countries.
The occurrence of 14 phthalate metabolites was found in human urine samples collected from seven Asian countries: China, India, Japan, Korea, Kuwait, Malaysia, and Vietnam. Phthalate metabolites were found in all samples, indicating widespread exposure of humans to phthalates in these Asian countries. The highest total (the sum of 14 phthalates) phthalate metabolite concentrations were found in samples collected from Kuwait (median: 1050 ng/mL), followed in decreasing order by samples from India (389 ng/mL), China (234 ng/mL), Vietnam (133 ng/mL), Japan (120 ng/mL), Korea (117 ng/mL), and Malaysia (94.9 ng/mL). The creatinine-adjusted median concentrations of total phthalates for urine samples from Kuwait, India, China, Vietnam, Japan, Korea, and Malaysia were 692, 506, 289, 119, 103, 104, and 169 μg/g creatinine, respectively. Monomethyl phthalate (mMP), monoethyl phthalate (mEP), mono (2-isobutyl phthalate) (miBP), mono-n-butyl phthalate (mBP), and metabolites of di-(2-ethylhexyl) phthalate (DEHP) were the dominant compounds, collectively accounting for >95% of the total concentrations in the samples from the seven countries. The profiles of urinary phthalate metabolite concentrations varied among the samples collected from the seven countries. Urine samples from Kuwait contained the highest concentrations of mEP (median: 391 ng/mL), mBP (94.1 ng/mL), and the metabolites of DEHP (202 ng/mL), whereas samples from China and Japan contained the highest concentrations of miBP (50.8 ng/mL) and mMP (17.5 ng/mL), respectively. mEP was the predominant metabolite in urine samples from India and Kuwait (accounting for 49% of the total), mBP and miBP were the predominant compounds in samples from China (52%), and DEHP metabolites were the predominant compounds in samples from Korea (46%) and Vietnam (52%). Based on the urinary concentrations of mEP, mBP, miBP, and DEHP metabolites of the samples from the seven Asian countries, we estimated daily intake rates of diethyl phthalate (DEP), dibutyl phthalate (DBP), and DEHP. The results indicated that people in the seven Asian countries are exposed to DEP, DBP, and DEHP at levels well below the reference doses (RfD) suggested as unsafe by the U.S. Environmental Protection Agency (EPA). The estimated exposure doses to DEHP in Kuwait, however, were above the RfD recommended by the EPA.
This paper presents the development of an emissions-controlling technique for oil burners aimed especially to reduce oxides of nitrogen (NOx). Another emission of interest is carbon monoxide (CO). In this research, a liquid fuel burner is used. In the first part, five different radial air swirler blade angles, 30 degrees , 40 degrees , 45 degrees , 50 degrees , and 60 degrees , respectively, have been investigated using a combustor with 163 mm inside diameter and 280 mm length. Tests were conducted using kerosene as fuel. Fuel was injected at the back plate of the swirler outlet. The swirler blade angles and equivalence ratios were varied. A NOx reduction of more than 28% and CO emissions reduction of more than 40% were achieved for blade angle of 60 degrees compared to the 30 degrees blade angle. The second part of this paper presents the insertion of an orifice plate at the exit plane of the air swirler outlet. Three different orifice plate diameters of 35, 40, and 45 mm were used with a 45 degrees radial air swirler vane angle. The fuel flow rates and orifice plate's sizes were varied. NOx reduction of more than 30% and CO emissions reduction of more than 25% were obtained using the 25 mm diameter orifice plate compared to the test configuration without the orifice plate. The last part of this paper presents tests conducted using the air-staging method. An industrial oil burner system was investigated using the air staging method in order to reduce emission, especially NOx. Emissions reduction of 30% and 16.7% were obtained for NOx and CO emissions, respectively, when using air staging compared to the non-air-staging tests.
Biodiesel from Jatropha curcas L. seed is conventionally produced via a two-step method: extraction of oil and subsequent esterification/transesterification to fatty acid methyl esters (FAME), commonly known as biodiesel. Contrarily, in this study, a single step in situ extraction, esterification and transesterification (collectively known as reactive extraction) of J. curcas L. seed to biodiesel, was investigated and optimized. Design of experiments (DOE) was used to study the effect of various process parameters on the yield of FAME. The process parameters studied include reaction temperature (30-60 degrees C), methanol to seed ratio (5-20 mL/g), catalyst loading (5-30 wt %), and reaction time (1-24 h). The optimum reaction condition was then obtained by using response surface methodology (RSM) coupled with central composite design (CCD). Results showed that an optimum biodiesel yield of 98.1% can be obtained under the following reaction conditions: reaction temperature of 60 degrees C, methanol to seed ratio of 10.5 mL/g, 21.8 wt % of H(2)SO(4), and reaction period of 10 h.
The occurrence of perfluorinated compounds (PFCs) in human blood is known to be widespread; nevertheless, the sources of exposure to humans, including infants, are not well understood. In this study, breast milk collected from seven countries in Asia was analyzed (n=184) for nine PFCs, including perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA). In addition, five brands of infant formula (n=21) and 11 brands of dairy milk (n=12) collected from retail stores in the United States were analyzed, for comparison with PFC concentrations previously reported for breast milk from the U.S. PFOS was the predominant PFC detected in almost all Asian breast milk samples, followed by perfluorohexanesulfonate (PFHxS) and PFOA. Median concentrations of PFOS in breast milk from Asian countries varied significantly;the lowest concentration of 39.4 pg/mL was found in India, and the highest concentration of 196 pg/mL was found in Japan. The measured concentrations were similarto or less than the concentrations previously reported from Sweden, the United States, and Germany (median, 106-166 pg/mL). PFHxS was found in more than 70% of the samples analyzed from Japan, Malaysia, Philippines, and Vietnam, at mean concentrations ranging from 6.45 (Malaysia) to 15.8 (Philippines) pg/mL PFOA was found frequently only in samples from Japan; the mean concentration for that country was 77.7 pg/mL. None of the PFCs were detected in the infant-formula or dairy-milk samples from the U.S. except a few samples that contained concentrations close to the limit of detection. The estimated average daily intake of PFOS by infants from seven Asian countries, via breastfeeding, was 11.8 +/- 10.6 ng/kg bw/ day; this value is 7-12 times higher than the estimated adult dietary intakes previously reported from Germany, Canada, and Spain. The average daily intake of PFOA by Japanese infants was 9.6 +/- 4.9 ng/kg bw/day, a value 3-10 times greater than the estimated adult dietary intakes reported from Germany and Canada. The highest estimated daily intakes of PFOS and PFOA by infants from seven Asian countries studied were 1-2 orders of magnitude below the tolerable daily intake values recommended by the U.K. Food Standards Agency.
The SO2 sorption capacity (SSC) of sorbents prepared from rice husk ash (RHA) with NaOH as additive was studied in a fixed-bed reactor. The sorbents were prepared using a water hydration method by slurrying RHA, CaO, and NaOH. Response surface methodology (RSM) based on four-variable central composite face centered design (CCFCD) was employed in the synthesis of the sorbents. The correlation between the sorbent SSC (as response) with four independent sorbent preparation variables, i.e. hydration period, RHA/CaO ratio, NaOH amount, and drying temperature, were presented as empirical mathematical models. Among all the variables studied, the amount of NaOH used was found to be the most significant variable affecting the SSC of the sorbents prepared. The SSC for sorbent prepared with the addition of NaOH was found to be significantly higher than sorbents prepared without NaOH. This is probably because NaOH is a deliquescent material, and its existence increases the amount of water collected on the surface of the sorbent, a condition required for sorbent-SO2 reaction to occur at low temperature. The effect of further treatment of RHA at 600 degrees C was also investigated. Although pretreated RHA sorbents demonstrated higher SSC as compared to untreated RHA sorbents, nevertheless, at optimum conditions, sorbents prepared from untreated RHA was found to be more favorable due to practical and economic concerns.
Mussel samples were used in this study to measure the levels of polybrominated diphenyl ethers (PBDEs) and organochlorines (OCs) in the coastal waters of Asian countries like Cambodia, China, Hong Kong, India, Indonesia, Japan, Korea, Malaysia, the Philippines, and Vietnam. PBDEs were detected in all the samples analyzed, and the concentrations ranged from 0.66 to 440 ng/g lipid wt. Apparently higher concentrations of PBDEs were found in mussels from the coastal waters of Korea, Hong Kong, China, and the Philippines, which suggests that significant sources of these chemicals exist in and around this region. With regard to the composition of PBDE congeners, BDE-47, BDE-99, and BDE-100 were the dominant congeners in most of the samples. Among the OCs analyzed, concentrations of DDTs were the highest followed by PCBs > CHLs > HCHs > HCB. Total concentrations of DDTs, PCBs, CHLs, and HCHs in mussel samples ranged from 21 to 58 000, 3.8 to 2000, 0.93 to 900, and 0.90 to 230 ng/g lipid wt., respectively. High levels of DDTs were found in mussels from Hong Kong, Vietnam, and China; PCBs were found in Japan, Hong Kong, and industrialized/urbanized locations in Korea, Indonesia, the Philippines, and India; CHLs were found in Japan and Hong Kong; HCHs were found in India and China. These countries seem to play a role as probable emission sources of corresponding contaminants in Asia and, in turn, may influence their global distribution.
Siliceous materials such as rice husk ash (RHA) have potential to be utilized as high performance sorbents for the flue gas desulfurization process in small-scale industrial boilers. This study presents findings on identifying the key factorfor high desulfurization activity in sorbents prepared from RHA. Initially, a systematic approach using central composite rotatable design was used to develop a mathematical model that correlates the sorbent preparation variables to the desulfurization activity of the sorbent. The sorbent preparation variables studied are hydration period, x1 (6-16 h), amount of RHA, x2 (5-15 g), amount of CaO, x3 (2-6 g), amount of water, x4 (90-110 mL), and hydration temperature, x5 (150-250 degrees C). The mathematical model developed was subjected to statistical tests and the model is adequate for predicting the SO2 desulfurization activity of the sorbent within the range of the sorbent preparation variables studied. Based on the model, the amount of RHA, amount of CaO, and hydration period used in the preparation step significantly influenced the desulfurization activity of the sorbent. The ratio of RHA and CaO used in the preparation mixture was also a significant factor that influenced the desulfurization activity of the sorbent. A RHA to CaO ratio of 2.5 leads to the formation of specific reactive species in the sorbent that are believed to be the key factor responsible for high desulfurization activity in the sorbent. Other physical properties of the sorbent such as pore size distribution and surface morphology were found to have insignificant influence on the desulfurization activity of the sorbent.
The coagulation-flocculation process incorporated with membrane separation technology will become a new approach for palm oil mill effluent (POME) treatment as well as water reclamation and reuse. In our current research, a membrane pilot plant has been used for POME treatment where the coagulation-flocculation process plays an important role as a pretreatment process for the mitigation of membrane fouling problems. The pretreated POME with low turbidity values and high water recovery are the main objectives to be achieved through the coagulation-flocculation process. Therefore, treatment optimization to serve these purposes was performed using jar tests and applying a response surface methodology (RSM) to the results. A 2(3) full-factorial central composite design (CCD) was chosen to explain the effect and interaction of three factors: coagulant dosage, flocculent dosage, and pH. The CCD is successfully demonstrated to efficiently determine the optimized parameters, where 78% of water recovery with a 20 NTU turbidity value can be obtained at the optimum value of coagulant dosage, flocculent dosage, and pH at 15 000 mg/L, 300 mg/L, and 6, respectively.
Perfluorooctanesulfonyl fluoride based compounds have been used in a wide variety of consumer products, such as carpets, upholstery, and textiles. These compounds degrade to perfluorooctanesulfonate (PFOS), a persistent metabolite that accumulates in tissues of humans and wildlife. Previous studies have reported the occurrence of PFOS, perfluorohexanesulfonate (PFHxS), perfluorooctanoate (PFOA), and perfluorooctanesulfonamide (PFOSA) in human sera collected from the United States. In this study, concentrations of PFOS, PFHxS, PFOA, and PFOSA were measured in 473 human blood/serum/plasma samples collected from the United States, Colombia, Brazil, Belgium, Italy, Poland, India, Malaysia, and Korea. Among the four perfluorochemicals measured, PFOS was the predominant compound found in blood. Concentrations of PFOS were the highest in the samples collected from the United States and Poland (>30 ng/mL); moderate in Korea, Belgium, Malaysia, Brazil, Italy, and Colombia (3 to 29 ng/mL); and lowest in India (<3 ng/mL). PFOA was the next most abundant perfluorochemical in blood samples, although the frequency of occurrence of this compound was relatively low. No age- or gender-related differences in the concentrations of PFOS and PFOA were found in serum samples. The degree of association between the concentrations of four perfluorochemicals varied, depending on the origin of the samples. These results suggested the existence of sources with varying levels and compositions of perfluorochemicals, and differences in exposure patterns to these chemicals, in various countries. In addition to the four target fluorochemicals measured, qualitative analysis of selected blood samples showed the presence of other perfluorochemicals such as perfluorodecanesulfonate (PFDS), perfluoroheptanoic acid (PFHpA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorododecanoic acid (PFDoA), and perfluoroundecanoic acid (PFUnDA) in serum samples, at concentrations approximately 5- to 10-fold lower than the concentration of PFOS. Further studies should focus on identifying sources and pathways of human exposure to perfluorochemicals.
The occurrence of n-alkanoic acids, amides, and nitriles in samples of aerosol particulate matter from Kuala Lumpur and Santiago suggests that emissions from cooking and biomass burning are the primary sources of these organic markers in the atmosphere. It is proposed that fatty acids react with ammonia during biomass burning or combustion to produce amides and nitriles, which can be applied as useful biomarker tracers. To test this hypothesis, nonadecanoic acid and hexadecanamide were used as reactants in hydrous pyrolysis experiments. These experiments produced amides and nitriles and indicated that ammonia is an essential agent in their formation. Thus amides and nitriles are of utility as indicators for input from combustion and biomass burning in the ambient atmosphere.
An isotopic dilution assay was developed to measure radiolabile As concentration in a diverse range of soils (pH 3.30-7.62; % C = 1.00-6.55). Soils amended with 50 mg of As kg(-1) (as Na2HAsO4 x 7H2O) were incubated for over 800 d in an aerated "microcosm" experiment. After 818 d, radiolabile As ranged from 27 to 57% of total applied As and showed a pH-dependent increase above pH 6. The radiolabile assay was also applied to three sets of soils historically contaminated with sewage sludge or mine-spoil. Results reflected the various geochemical forms in which the arsenic was present. On soils from a sewage disposal facility, radiolabile arsenate ranged from 3 to 60% of total As; mean lability was lower than in the equivalent pH range of the microcosm soils, suggesting occlusion of As into calcium phosphate compounds in the sludge-amended soils. In soils from mining areas in the U.K. and Malaysia, radiolabile As accounted for 0.44-19% of total As. The lowest levels of lability were associated with extremely large As concentrations, up to 17,000 mg kg(-1), from arsenopyrite. Soil pore water was extracted from the microcosm experiment and speciated using "GEOCHEM". The solid<==>solution equilibria of As in the microcosm soils was described by a simple model based on competition between HAsO4(2-) and HPO4(2-) for "labile" adsorption sites.
This is the first report on fecal pollution using molecular markers in Southeast Asia where serious sewage pollution has occurred. A simple and sensitive analytical method using gas chromatography-mass spectrometry for 10 sterols in various environmental samples was developed to monitor extensive areas of tropical Asia. First, the method was applied to wastewater to confirm that >95% of sterols existed in the particulate phase. Then the approach was applied to a tropical Asian region, Malaysia and Vietnam, with a selection of 59 sampling stations in total. River water and sediment samples were collected and analyzed for chemical markers (coprostanol and other sterols) and microbiological markers (fecal coliforms and fecal streptococci). Particulate coprostanol concentrations ranged from <0.0001 to 13.47 microg/L in tropical river and estuarine waters, indicating severe fecal pollution in populous areas. Coprostanol concentrations in the sediments ranged from 0.005 to 15.5 microg/g-dry. The sedimentary coprostanol concentrations were lower than those reported in some urban areas of industrialized countries. This is probably because frequent heavy rain induces intensive input of eroded soil, which dilutes fecal material in river sediments. The relationship between the concentrations of fecal sterols and bacterial indicators was examined in an attempt to develop public health criteria for coprostanol levels applicable to the tropical region. Coprostanol concentrations of 30-100 ng/L or percent coprostanol levels of 2% corresponded to approximately 1000 fecal coliforms per 100 mL, which is set for secondary contact limit in many countries. These coprostanol concentrations were lower than those proposed as criteria in temperate countries, probably owing to greater survival of bacteria in warmer tropical waters. On the basis of these criteria, extensive monitoring of sediments suggests that poor sanitary conditions exist in most of the urbanized area of Malaysia and in several urban and rural sites in Vietnam.
This is the first publication on the distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in riverine and coastal sediments in South East Asia where the rapid transfer of land-based pollutants into aquatic environments by heavy rainfall and runoff waters is of great concern. Twenty-nine Malaysian riverine and coastal sediments were analyzed for PAHs (3-7 rings) by gas chromatography mass spectrometry. Total PAHs concentrations in the sediment ranged from 4 to 924 ng/g. Alkylated homologues were abundant for all sediment samples. The ratio of the sum of methylphenanthrenes to phenanthrene (MP/P), an index of petrogenic PAHs contribution, was more than unity for 26 sediment samples and more than 3 for seven samples for urban rivers covering a broad range of locations. The MP/P ratio showed a strong correlation with the total PAHs concentrations, with an r2 value of 0.74. This ratio and all other compositional features indicated that Malaysian urban sediments are heavily impacted by petrogenic PAHs. This finding is in contrast to other studies reported in many industrialized countries where PAHs are mostly of pyrogenic origin. The MP/P ratio was also significantly correlated with higher molecular weight PAHs such as benzo[a]pyrene, suggesting unique PAHs source in Malaysia which contains both petrogenic PAHs and pyrogenic PAHs. PAHs and hopanes fingerprints indicated that used crankcase oil is one of the major contributors of the sedimentary PAHs. Two major routes of inputs to aquatic environments have been identified: (1) spillage and dumping of waste crankcase oil and (2) leakage of crankcase oils from vehicles onto road surfaces, with the subsequent washout by street runoff. N-Cyclohexyl-2-benzothiazolamine (NCBA), a molecular marker of street dust, was detected in the polluted sediments. NCBA and other biomarker profiles confirmed our hypothesis of the input from street dust contained the leaked crankcase oil. The fingerprints excluded crude oil, fresh lubricating oil, asphalt, and tire-particles as major contributors.