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Previous animal studies provided the evidence that prenatal titanium exposure can cause neurotoxicity in their offspring, while human data is vacant. Our aim was to identify the associations of prenatal titanium exposure with the child neurodevelopment. Participants in present study were recruited during early pregnancy between 2014 and 2017. Urinary concentrations of titanium at first trimester were determined. We assessed child neurodevelopment using the Chinese version of Gesell Developmental Schedules at first year follow-up. The multivariable linear regressions and the robust modified Poisson regressions were used to estimate the associations of specific gravity corrected urinary titanium concentrations with the child neurodevelopment. In adjusted models, children's developmental quotient scores in the language domain were 2.03 points (95% CI: -3.66, -0.40) lower in the highest tertile of prenatal urinary titanium than in the lowest tertile. Also, children with prenatal urinary titanium in the highest tertile had 1.42 times (95% CI: 1.17, 1.72) increased risk of language development delay compared to those in the lowest tertile. No statistically significant associations were observed between titanium exposure and child development delay in motor, adaptive and social areas. The findings indicated that prenatal higher titanium exposure was associated with impaired language development, suggesting that titanium might act as developmental neurotoxicants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

A convenient technique for direct solids analysis, laser ablation single particle aerosol mass spectrometry (LA-SPAMS), was used to investigate lead and other components in soil and bark samples from around a battery industrial park. In total, over 50,000 particles ranging in size from 0.2 to 2 μm were sampled and approximately 15-35% of the particles were analyzed for chemical composition. The mean mass spectrum results showed that the intensity of lead varied widely among sampling points, reaching the highest intensity in the topsoil and bark at sampling point 4, located closest to the core factory. Based on the neural network algorithm of adaptive resonance theory (ART-2a), the topsoil and bark samples were classified into five categories: crustal composition (Ca + , silicates, aluminates, etc.), elemental carbon (C 2 - , C 3 - , C 4 - , etc.), organic carbon (CN - , levoglucosan, etc.), secondary inorganic sources (phosphates, nitrates, sulfates), and heavy metals (Pb + , Zn + , Cu + ), with the proportion of Pb varying from 0.020 to 0.25% and 0.030-9.41% in topsoil and bark samples, respectively, while the proportion of Cu and Zn in topsoil and bark samples did not differ as greatly as Pb. In addition, the particle number concentrations of lead particles in topsoil and bark ranged from 0.14 to 3.48% and 0.36-37.93%, respectively. The concentrations of Pb in topsoil and bark samples measured by ICP-OES varied from 71 to 791 ppm and 172-2595 ppm, respectively. Overall, both the lead content in topsoil samples measured by LA-SPAMS and ICP-OES reached maximum values at sampling points 4 and 5, respectively, indicating moderate pollution with Pb at these two sites. This convenient LA-SPAMS method not only accurately detects the composition of solid samples, the mixing state of particulate matter, and the analytical component sources, but also omits tedious pretreatment steps, reduces the use of organic solvents, and shortens the detection time of solid samples, thereby providing an attractive method for soil environmental quality monitoring., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Gaseous and particulate nitrated polycyclic aromatic hydrocarbons (NPAHs, 12 species) and oxygenated polycyclic aromatic hydrocarbons (OPAHs, 4 species) in seven coastal cities of the Bohai and Yellow Seas were determined throughout the year. The annual arithmetical mean concentrations of ΣNPAH 12 and ΣOPAH 4 were 737 ± 475 pg/m 3 and 35.3 ± 26.8 ng/m 3 . NPAHs and OPAHs existed mainly in the gaseous phase, accounted for 88.5% and 95.2% of the total concentrations. Air concentrations of ΣNPAH 12 and ΣOPAH 4 in the coastal cities of the Yellow Sea were significantly lower (p < 0.05) than those of the Bohai Sea. Air concentrations of ΣNPAH 12 and ΣOPAH 4 were significantly higher (p < 0.01) in winter than in summer. Strong secondary formation of atmospheric NPAHs and OPAHs occurred in all of the studied cities. The sequence of annual contribution of the emission sources of airborne NPAHs determined by positive matrix factorization was traffic exhaust > combustion of solid fuels (coal and biomass) > secondary formation, while for OPAHs, it was combustion of solid fuels > secondary formation > traffic exhaust. The combustion of solid fuels served as the main source of NPAHs and OPAHs in winter, while secondary formation was the predominant source in summer. Interregional transport may exert an important effect on the local atmospheric NPAHs and OPAHs by potential source contribution function analysis. The estimated incremental lifetime cancer risk (ILCR) due to inhalation exposure to specific NPAHs ranged from 2.9 × 10 -12 to 6.2 × 10 -6 (median at 4.8 × 10 -9 ) was mainly attributed to exposure before the age of 16., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Atmospheric coarse particulate matter (PM 10 ) enriched with heavy metal(loid)s could pose potentially significant health risk to humans, while accurate health risk assessment calls for characterization of their bioaccessibility, besides the total contents. The health risk of major toxic heavy metal(loid)s in the PM 10 from four large cities in northern China via inhalation was investigated based on their total contents and bioaccessibility. The annual mean concentrations of PM-bound Zn, As, Pb, and Mn in the atmosphere of the four cities were 650, 305, 227, and 177 ng⋅m -3 , respectively. The levels of heavy metal(loid)s in the PM 10 were generally higher in winter but lower in summer in all four cities, which resulted primarily from the emissions associated with coal combustion for district and household heating and the unfavorable meteorological conditions in winter. The bioaccessibility of heavy metal(loid)s in the PM 10 ranged from 0.9 to 48.7%, following the general order of Mn > Co > Ni > Cd > Cu > As > Cr > Zn > Pb. Based on their total contents in the PM 10 , most heavy metal(loid)s posed significant public health risk via inhalation exposure in the four cities. However, after accounting for the bioaccessibility of metal(loid)s, the non-carcinogenic risk of most metal(loid)s was negligible, except for As in the PM 10 of Jinzhong, while only the carcinogenic risk posed by Cr and As in the PM 10 exceeded the acceptable level. These findings demonstrate the importance of characterizing the bioaccessibility of airborne PM-bound heavy metal(loid)s in health risk assessment and could guide the on-going efforts on reducing the public health risk of PM 10 in northern China., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The surface products have a significant influence on the reactivity of zero-valent iron-based materials. Although the enhancing effect of graphene on the reactivity of nanoscale zero-valent iron (NZVI)/graphene composites have been confirmed, the effect of graphene on the formation of surface products of NZVI is not well understood. In order to assess the effect of graphene on the structural of the outer iron oxide layers of NZVI, the NZVI was pre-oxidized by graphene oxide (ONZVI-GO). Compared with the NZVI oxidized by O 2 (ONZVI-O 2 ), ONZVI-GO was shown to be effective at NO 3 - removal with a high efficiency over a wide range of initial pH values. The results from characterization showed that GO could induce the formation of a tight iron oxide shell with dense spinel structures. The boron introduced during the preparation of NZVI was doped into iron oxides on the surface of ONZVI-GO. The B-O in adsorbed borate was transformed to B-B/B-Fe in the lattice structure of iron oxides, causing the formation of highly electron-deficient Lewis acid sites on the surface of ONZVI-GO, which could effectively gather NO 3 - and OH - , leading to the higher efficiency removal of NO 3 - than ONZVI-O 2 over a wide range of initial pH values. This study provides new insight into the interaction between graphene and the surface species of NZVI., Competing Interests: Declaration of interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Sewage sludge dewatering is an efficient approach to reduce the volume of sludge for the subsequent disposal. In this study, a novel one-step acidification sludge dewatering method was developed with using oxalic acid as a conditioner. In laboratory-scale experiments with the dosage of 200 mg/g dry solid (DS), the normalized capillary suction time and the specific resistance to filtration were respectively decreased by 78.7% and 60.0% after 30 min of oxalic acid conditioning, much more efficient than those conditioned with sulfuric acid and hydrochloric acid at the same pH value. This superior dewatering performance was attributed to two factors. One was that oxalic acid could more efficiently promote the hydrolysis of polysaccharide, especially pectins, to release bound water. The other was that OA could dissolve more Fe 3+ and Al 3+ , as well as form precipitate with Ca 2+ in sludge, which may act as flocculants or co-precipitator for the subsequent sludge particles coagulation. In pilot-scale experiments, the water content of oxalic acid conditioned sludge cake was reduced to 60% under the optimum conditions, while the reagent cost was as low as 110.0 USD/t DS. This work provides a cost-effective and easy-operated sewage sludge disposal technique, and also sheds light on the potential of oxalic acid in environmental waste treatment., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Emission factors (EFs) of polycyclic aromatic hydrocarbon (PAH) derivatives (12 nitro-PAHs and 4 oxy-PAHs) during the pyrolysis of two types of electronic waste (E-waste) were measured. Compositional profile, particle size distribution, gas-particle partitioning, correlations with precursor species and influences of pyrolytic temperature were investigated. The derivative products were dominated by oxy-PAHs. The averaged EFs of oxy-PAHs were 3.37 ± 4.10 μg/g and 32.6 ± 18.1 μg/g for PWBs and plastic casings, respectively, and those of nitro-PAHs were 85.7 ± 92.4 ng/g and 83.3 ± 69.7 ng/g, respectively. Most EFs of derivative species significantly correlated with their corresponding parent PAHs (p < 0.05), except a few cases, indicating formation of derivatives via related reactions of parent species. Most nitro-PAHs occurred in fine particles with the size < 2.1 μm, and oxy-PAHs were prevailing in fine particles with the size between 0.4 μm and 2.1 μm. Proportions of oxy-PAHs in particulate phase, especially those with higher molecular weight, were noticeably greater than those of the corresponding parent species. Below 480 °C, there was no evident difference in the EFs of PAH derivatives, while the EFs noticeably increased from 520 °C. With the increasing temperature, the majority of oxy-PAHs still occurred on finer particles, while the contribution of coarser particles tended to increase., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In this study, the mechanism that lithium (Li) promotes the production of reactive oxygen species (ROS) via the glycogen synthase kinase-3β (GSK-3β)/tuberous sclerosis complex 2 (TSC2)/target of rapamycin (TOR) signaling was investigated in the gill of zebrafish (Danio rerio). After the zebrafish were treated by 25 and 50 mg/L Li + , the mRNA expression of GSK-3β and TSC2 was inhibited, but the expression of TOR was induced in the gill of zebrafish. The levels of hydrogen peroxide (H 2 O 2 ), superoxide anion (O 2 ·- ), and hydroxy radical (·OH) as well as the activity of superoxide dismutase (SOD) were increased, while the activities of catalase (CAT), glutathione peroxidase (GSH-PX), and peroxidase (POD) were decreased by 25 and 50 mg/L Li + treatments. In the ZF4 cells, the mRNA expression of GSK-3β and TSC2 was inhibited, but TOR expression was induced by 1, 5, and 10 mmol/L Li + treatments. To further confirm that lithium promoted ROS production via GSK-3β inhibition, GSK-3β RNA was interfered. It was found that the interference of GSK-3β RNA induced the TSC2/TOR signaling. The levels of H 2 O 2 , O 2 ·- , and ·OH were increased, but the activities of CAT, GSH-PX, and POD were decreased by GSK-3β RNA interference. In addition, lithium decreased the mitochondrial membrane potential (MMP) with Rhodamine-123 assay, but increased the levels of ROS by 2',7'-dichlorofluorescein diacetate (DCFH-DA) assay. The present results indicated that lithium promoted the ROS production through the GSK-3β/TSC2/TOR signaling in the gill of zebrafish., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

243 surface soil samples were collected from the Yangtze River Delta (YRD) region, and the concentration distributions and compositional profiles of 27 parent PAHs (PPAHs), nitro- and oxy-derivatives (NPAHs and OPAHs), respectively, and health risk of 16 PPAHs were determined. Atmospheric samples were collected at two sites with high topsoil concentrations of PAHs to assist in identifying the emission sources of PPAHs. The total concentrations of PPAHs, NPAHs and OPAHs fell in the ranges of 21.0-3563.2 ng/g, 0.4-4.6 ng/g and 2.1-834.1 ng/g, respectively. PPAHs in topsoil were dominated by low and medium molecular weight species. The main components of OPAHs were 9FO and ANQ. For NPAHs, only 1N-NAP was frequently detected. Overall, the northern parts of the YRD region were more heavily contaminated by PPAHs and their corresponding derivatives. The soil TOC fraction and GDP per capita were significantly correlated with the spatial distribution of PPAHs. Specific ratios of isomeric species and principal component analysis (PCA) designated combustion of industrial coal and biomass, and traffic exhaust as the main mixed emission sources of PPAHs in surface soils in this region. The detected NPAHs and OPAHs were significantly associated with the corresponding PPAHs. The estimated incremental lifetime cancer risk attributed to 16 PPAHs in surface soil was greater than 10 -6 , indicating a potential risk of contracting cancer by exposure to topsoil from the YRD region. The cumulative probability of cancer risk for both adults and children via three exposure pathways followed the sequence of dermal contact > ingestion > inhalation., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Bisphenol A (BPA) is widely spread in the environment, and can cause various reproductive disrupting effects on different organisms, including fish. Our previous published study showed that BPA has non-monotonic (inverted U-shaped) dose-response effect on rare minnow Gobiocypris rarus ovarian weight at different concentrations. To investigate the potential mechanism, we exposed female rare minnow to 1, 15 and 225 µg L(-1) BPA for 7 days in the present study. The levels of vitellogenin (Vtg), sex hormones, hydrogen peroxide (H2O2), glutathione (GSH) and triglyceride (TG) were measured. RNA-seq of ovary tissues was also performed. Result showed that Vtg, sex hormone and TG levels showed an inverted U-shaped increased response, while H2O2 and GSH levels showed a U-shaped inhibited response. RNA-seq data showed that many genes involved in lipid metabolism, oxidative stress, and proteolysis processes were altered. The change of Vtg, H2O2, GSH and TG levels was possibly related to the altered sex hormone levels. Sex hormone's direct effect, Vtg accumulation, TG accumulation and oxidative stress induced proteolysis may contribute to the change of ovary weight., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

There is wide concern about polycyclic aromatic hydrocarbons (PAHs) because of their carcinogenic and mutagenic potential. The coking industry is an important source of PAHs. In this study, 36 arable soil samples, a sensitive medium from the perspective of food safety and health, were collected from one of the largest coke production bases in China. The concentration of total 21 PAHs ranged from 294 to 1665 ng g(-1), with a mean of 822±355 ng g(-1). Approximately 60% of the soil samples were heavily polluted with the level higher than 600 ng g(-1). Particularly high abundances of high molecular weight PAHs were found, and the calculated BaPeq was as high as 54.3 ng g(-1). Soil PAH levels were positively correlated with soil organic matter content. The soil PAHs were from complex mixture sources, and high-temperature pyrogenic sources were most likely responsible for the heavy PAH contamination. Effective control strategies and probable remediation approaches should be proposed to improve soil quality., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The temporal trends in daily dietary exposure of the populations in Beijing and Shenyang, China to DDTs and HCHs through consumption of various food categories and the associated health risks were investigated in this work. The estimated dietary intakes of DDTs and HCHs in 2005/2007 were almost one and two orders of magnitude lower than those in 1992 and in the 1970s, respectively, revealing the historical decrease of DDT and HCH in Chinese foods after their applications were banned. The relative contributions of different foodstuffs to the overall intakes of DDTs and HCHs in the 1970s and in 1992 were very different from those in 2005/2007, mainly due to the remarkable concentration variance in foodstuffs and changes in diet habit of population. According to the hazard guidelines, it is concluded that intakes of these two pesticides in 2005/2007 may not exert adverse effects on human health., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The sorption coefficients obtained in field investigation vary greatly from laboratory sorption experiments. The possible reasons were discussed in literature. Observing the commonly reported desorption hysteresis, this study proposed that the unclear sorption history of the field study could also result in the diverse sorption coefficients. This study conducted a comparative study regarding phenanthrene sorption/desorption behavior in low-concentration multi-time sorption process and the commonly applied high-concentration one-time sorption process. The sorption coefficients determined during the desorption process were much higher than those at sorption process. Thus, the prediction of sorption coefficient should be related with sorption history. Desorption hysteresis was increased with increased equilibration time and decreased solid-phase concentration. In addition, although the apparent contact time between sorbate and sorbent was shorter for low-concentration multi-time sorption, the desorption hysteresis was much stronger, which consequently result in higher sorption coefficients in comparison to high-concentration one-time sorption. Pore swelling or diffusion-controlled sorption kinetics could not explain this phenomenon. This study calls for research attention on sorption history, especially for field investigations., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Oral ingestion of contaminated soil is an important pathway of human exposure to hydrophobic organic contaminants (HOCs), particularly for children in developing countries. The mobilization potential of various contaminants from ingested soil is often characterized using an in vitro gastrointestinal model, based on the quantities of contaminants remaining in digestive fluid after digestion and separation. Recently, it was experimentally demonstrated that a large fraction of mobilized contaminants sorbed on the digested residue could be released if the dissolved fraction was removed by intestinal absorption. This hypothesis was further tested in this study. Soil spiked with dichlorodiphenyltrichloroethane and its metabolites (DDXs) and polycyclic aromatic hydrocarbons (PAHs) was digested using an in vitro gastrointestinal model. A human colon carcinoma cell line (Caco-2) was cultured in digestive fluid with or without soil residue (pre-equilibrated with the soil) for 2h. A large proportion of the contaminants (37-68%) was sorbed on the digested residue. Without this residue, 66±13% of DDXs and 73±14% of PAHs dissolved in the fluid, as means and standard deviations, were absorbed by the cell monolayer after exposure. With both digestive fluid and residue, the sorbed fraction of PAHs and DDXs decreased by 38-92%, while the ratios of the cellular to the dissolved concentrations were 2.7-2.8 times higher than those without the residue. This supported the hypothesis that the cell absorption of dissolved HOCs induces desorption of the sorbed fraction from digestive residue, and the desorbed HOCs can be absorbed as well., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Japanese Rabbits (Oyctolagus cuniculus) were exposed to α-hexachlorocyclohexane (α-HCH) either orally or dermally and concentrations of α-HCH and its two enantiomers were measured at different time intervals in the blood, intestine, liver, kidney, fat, brain, and muscle. The time trends were quantified using toxicokinetic models. It was found that absorption and elimination of α-HCH in blood were first-order processes which can be characterized by a single compartmental kinetic model. The absorption of dermally exposed α-HCH in blood was more than one order of magnitude faster than that of orally exposed α-HCH. The transport of α-HCH from the blood to other tissues was characterized using a two-compartment model. The accumulation rates were different among tissues depending on blood flow rate and fat content. Significant correlation was revealed between α-HCH concentration and fat content for various tissues either before or 1 d after the exposure. However, there was no such correlation at 10 min immediately after the exposure. The enantiomeric fraction (EF) of α-HCH in rabbit blood was nearly racemic before the exposure and increased to 0.73 and 0.82 after oral or dermal exposure, respectively. The result of a toxicokinetic modeling suggested that the strong enantioenrichment of (+)-α-HCH was primarily because the elimination rate of (-)-α-HCH was more than two times higher than that of (+)-α-HCH. The EFs for other tissues also increased dramatically after the exposure and the EFs in brain reached as high as 0.99 due to enantioselective transport across the blood brain barrier., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

Although linear binding isotherms of hydrophobic organic chemicals (HOCs) with dissolved organic matter (DOM) are widely reported, several studies showed nonlinear HOC-DOM interactions. This study pointed out that fluorescence static quenching modeling (FSQM), which often uses a Stern-Volmer type plot to process the data from fluorescence quenching experiments, is conceptually different from the classic Stern-Volmer equation. We also emphasized that although linear Stern-Volmer plots are generally observed in literature, it does not necessarily indicate a linear HOC-DOM interaction. According to both mathematical simulation and laboratory sorption experiments in this study, nonlinear interactions could be concealed by the use of Stern-Volmer plot. Moreover, this study tested the two assumptions for applying FSQM to process binding data. Our results showed that binding coefficient (K(DOC)) for phenanthrene is neither independent of free solute concentration, nor DOM concentration, which is a critical limitation for using FSQM in a form of Stern-Volmer equation to examine HOC-DOM interactions. Therefore, the true characteristics of HOC-DOM interactions need to be examined using different ways of experimental design and data processing.

The sorption coefficient, K(OC), of phenanthrene (PHE) has been reported to vary with different types of organic matter, leading to uncertainties in predicting the environmental behavior of PHE. Among the studies that relate organic matter properties to their sorption characteristics, physical conformation of organic matter is often neglected. In this work, organic matter samples of different physical forms were examined for their sorption characteristics. Dissolved humic acids (DHA) showed significantly higher K(OC) than the corresponding solid humic acids (SHA) from which the DHAs were made. The K(OC) of DHAs was found to be related to polarity, whereas K(OC) of SHAs increased with aliphatic carbon content. Soil particles were treated with H(2)O(2) to remove organic matter, and humic acid was coated on H(2)O(2)-treated soil particles to make organo-mineral complexes at pH 4, 7 and 10. Although the nonlinear sorption was apparent for SHAs and H(2)O(2)-treated soil particles, the organo-mineral complexes formed using these two components at pH 4, 7 and 10 exhibited relatively linear sorption at organic carbon content, f(OC)>0.5%. These results indicate that organic matter of the same composition may have different sorption properties due to different physical forms (or conformations). Nonlinear sorption for the complexes formed at pH 4 with lower f(OC) (<0.5%) was also discussed.

Water, suspended solid (SS) and sediment samples were collected from nine water courses in Tianjin, China and analyzed for dichlorodiphenyltrichloroethane (DDT) and its metabolites (DDXs, including o,p'-,p,p'-DDT, DDD and DDE). The average DDX concentrations in water, SS and sediment were 59+/-30 ng l(-1), 2690+/-1940 ng g(-1)dry wt. and 340+/-930 ng g(-1)dry wt., respectively. Due to the termination of the extensive agricultural application and industrial manufacture, DDXs in river sediment decreased by one order of magnitude since 1970's and low DDT fractions in these sediments were observed. Still, DDXs in the sediments near the outlets of the major manufacturers remained relatively high attributed to the historic input. DDXs in sediment were also positively correlated with organic matter content. Spatial distributions of DDXs in SS and water was different from that in sediment. For SS, a negative correlation between DDX concentration and SS content indicated a dilution effect in many rivers. Dissolved organic carbon content was the major factor affecting DDX concentrations in water phase. Wastewater discharged from dicofol manufacturers and likely illegal agricultural application were the primary reasons causing high DDT (DDE+DDD) ratios in SS and water.

A dynamic fugacity model was applied to simulate the changes of contents and transfer fluxes of hexachlorocyclohexane (HCHs) and dichloro-diphenyl-trichloroethane (DDTs) from 1950s in the environment of Hangzhou, China. The receptors are composed of air, surface water, soils, sediment and biota compartments. The model provides a method to combine loadings of HCHs and DDTs from various sources with a series of physical-chemical processes to estimate concentrations and transport fluxes of HCHs and DDTs. Model results suggested that the calculated concentrations were in line with the observed ones. The highest contents of HCH and DDT in the environment of study area were 523 t and 471 t before 1983, among which about 80.7% HCHs and 93.2% DDTs remained in the soil compartment. From 1984 to now, contents of HCHs and DDTs had decreased to about 0.07% and 0.40% of their highest amount (before 1983), and only about 0.001% and 0.014% will expect to be left in 2020 in the study area according to the model prediction. Before 1983, the main transfer fluxes of HCHs were deposition from air to soil, runoff from soil to water and diffusion from soil to air, but for DDTs the main transfer fluxes were deposition from air to soil and water, and transfer from water to sediment. From 1984 to now, runoff from soil to water and transfer from water to sediment became the dominant processes. Although a large amount of HCHs and DDTs had been applied to the study area, their residue levels in the soils were much lower than those in North China (had lesser HCHs and DDTs application than in South China) at present time, and close to other locations of South China (had similar HCHs and DDTs application level). It can be attributed to the high precipitation and temperature that enhances the processes of wet deposition, evaporation and degradation of OCPs. Sensitivities of the input parameters to the calculated concentrations were evaluated using coefficient-of-variation normalized sensitivity coefficients. The model was also subjected to uncertainty analyses using a Monte Carlo simulation.

Exposure of on-duty traffic police in Beijing to polycyclic aromatic hydrocarbons (PAHs) was investigated during the summer, 2004 using a personal sampling technique in measuring both particulate and gaseous phase PAHs. The results were then compared with those from two control sites away from the street. Exposure levels to gaseous and particulate PAHs for the traffic police were found to be 1525 +/- 759 ngm(-3) and 148 +/- 118 ngm(-3), respectively, representing 2-2.5 times higher levels than those at the control sites. The daily inhalation exposure of the police was estimated to be 277 ngkg(-1)d(-1). Most of the PAHs exposure came from the vapor phase, particularly NAP, FLO and PHE. Based on calculated PAH diagnostic ratios, the major source of PAHs exposure was from vehicle exhaust. The effects of temperature, humidity and atmospheric stability on exposure levels are also discussed.

A new method was proposed to determine pyrene in mucus, which combined the synchronous fluorimetry with the multiple standard addition method (SFMSA). The method was used to determine pyrene in mucus directly without pretreatment. The method detection limit (MDL) for pyrene in mucus was measured as 0.47 ng/ml with a relative standard deviation of 12.7% (n = 7). The standard addition graph was linear in the range 0.05-50.00 ng/ml (r(2) = 0.9989). SFMSA was validated using a GC/MS method as a reference method, and nice agreement was found. The pyrene in mucus can be directly monitored by SFMSA without solvent extraction of samples. This indicates that SFMSA is more timesaving, less laborious and cheaper than the GC/MS method with solvent extraction. SFMSA has lower MDL and higher average recovery than the GC/MS method.

Sorption behavior of hydrophobic organic contaminants (HOCs) (i.e., pyrene, phenanthrene and naphthalene) by native and chemically modified biopolymers (lignin, chitin and cellulose) was examined. Lignins (native and treated) showed nonlinear sorption for all compounds studied, emphasizing their glassy character. Chitins and celluloses had linear isotherms for phenanthrene and naphthalene, illustrating the dominance of partitioning, while pyrene yielded nonlinear isotherms. Sorption capacity (K(oc)) of HOCs was negatively correlated with the polarity [(O+N)/C] of the biopolymers. Aromatic and alkyl+aromatic C percentages, rather than alkyl C content, demonstrated a better correlation with K(oc) values, indicating the importance of aromatic structures for HOC affinity. Hydrophobicity (K(ow))-normalized K(oc) values decreased sharply with increasing percentage of O-alkyl C versus total aliphatic C (O-alkyl C/total aliphatic C) or with polar C/(alkyl+aromatic C) ratio of the biopolymers until their values reached 80% and 4, respectively, illustrating the effect of surrounding polar groups on reducing affinity for HOCs. Overall, the results of this study highlight the role of spatial arrangement of domains within biopolymers in sorption of HOCs, and point to sorbent properties, such as functionality, polarity and structure, jointly regulating the sorption of HOCs in biopolymers.

Soil cores were collected from soils at five sites in Tianjin area for the determination of hexachlorocyclohexane isomers (HCHs, including alpha-HCH, beta-HCH, gamma-HCH and delta-HCH), dichlorodiphenyltrichloroethane and metabolites (DDXs, including p,p'-DDT, p,p'-DDE and p,p'-DDD) and total organic carbon (TOC). The levels and vertical distributions of HCHs and DDXs are studied. Results show that the application of pesticides in the past years was the major contributor of HCHs and DDXs accumulation in the sampling areas. Significant positive correlations were seen between the residual and application amounts of HCHs and DDXs. Wastewater irrigation did not bring a significant contribution of HCHs or DDXs into the soils. HCHs and DDXs concentrations peak at the surface and decline in soil profile with depth, while fluctuations were observed in the plow layers of some cultivated soils caused by frequent cultivation activities and batch irrigation. Positive correlations were observed between the contents of TOC and HCHs and DDTs. Although the amounts of HCHs application in all sampling sites are larger than DDXs, at surface and near surface layers of most sampling sites, the concentrations of summation operatorHCHs are lower than summation operatorDDXs. The composition of DDXs in the applied pesticides and sampled soils indicates that there is no recent DDT input at the sample areas.

The size distributions of 16 polycyclic aromatic hydrocarbons (PAHs) and particle mass less than 10 microm in aerodynamic diameter (Dp) were measured using a nine-stage low-volume cascade impactor at rural and urban sites in Tianjin, China in the winter of 2003-2004. The particles exhibited the trimodal distribution with the major peaks occurring at 0.43-2.1 and 9.0-10.0 microm for both urban and rural sites. The concentrations of the total PAH (sum of 16 PAH compound) at rural site were generally less than those of urban site. Mean fraction of 76.5% and 63.9% of the total PAH were associated with particles of 0.43-2.1 microm at rural and urban sites, respectively. Precipitation, temperature, wind speed and direction were the important meteorological factors influencing the concentration of PAHs in rural and urban sites. The distributions of PAHs concentration with respect to particle size were similar for rural and urban samples. The PAHs concentrations at the height of 40 m were higher than both of 20 and 60 m at urban site, but the mass median diameter (MMD) of total PAH increased with the increasing height. The mid-high molecular weight (278 >or= MW >or= 202) PAHs were mainly associated with fine particles (Dp or=MW >or=178) PAHs were distributed in both of fine and coarse particle. The fraction of PAHs associated with coarse particles (Dp>2.1 microm) decreased with increasing molecular weight. The relatively consistent distribution of PAHs seemed to indicate the similar combustion source of PAHs at both of rural and urban sites. The fine differences of concentration and distribution of PAHs at different levels at urban site suggested that the different source and transportation path of particulate PAHs.

The characterization of the Chlorella vulgaris solution was carried out using synchronous-scan spectroscopy. The range of concentration of algae and Fe(III) in aqueous solutions were 5 x 10(8)-8 x 10(9) cells l(-1) and 10-60 microM, respectively. Effective characterization method used was synchronous-scan fluorescence spectroscopy. The wavelength difference (Deltalambda) of 90 nm was maintained between excitation and emission wavelengths; 90 nm was found to be the best Deltalambda for effective characterization of Chlorella vulgaris solution with or without quencher species (e.g., Fe(III), humic acid (HA)) for the first time. The peak was observed at about EX 236.6 nm/EM 326.6 nm for synchronous-scan fluorescence spectra. The fluorescence quenching of algae in system of algae-Fe(III)-HA was studied using synchronous-scan spectroscopy for the first time. Fe(III) was clearly the effective quencher. The relationship between I0/I (quenching efficiency) and c (concentration of Fe(III) added) was a linear correlation for the algae solution with Fe(III). Also, Aldrich humic acid was found to be an effective quencher. pH effect on synchronous-scan fluorescence intensity of algal solution with Fe(III) and/or HA was evident.

The dynamic exposures to HCHs of individuals born between the years 1913 and 1993 in Tianjin have been simulated by connecting a fugacity model (IV) with a multimedia exposure model. Ingestion is the most important pathway for human beings to take up HCHs, and concentrations in the human body correlate with body weight changes. Accumulations of HCHs were derived assuming that the degradation in human body behaved linearly. The health risk of exposure to HCHs was measured using cancer risk and loss of life expectancy (LLE), and LLE was modified from its original definition to incorporate a dynamic calculation that takes variances in exposure into account. Monte-Carlo simulations were run to analyze the uncertainties of the model.

A Monte Carlo simulation for uncertainty analysis of three key parameters (local coal consumption rate Q(1L), dry deposition velocity of aerosol particulate Kp and biodegradation rate of benzo(a)pyrene in soil and sediment K(R3)) was conducted in this study. Results of the simulation indicate that the three parameters were influenced by uncertainty and that all equilibrium concentrations in the four bulk compartments and various sub-compartments were log-normally distributed. However, the results also indicated that among the six primary transfer fluxes, erosion associated with solids in soil and deposition associated with solids in water, along with output from sewers were also log-normally distributed, while deposition from air to soil and biodegradation in soil and sediment followed normal distributions. The effect of uncertainty on the model results of the three key parameters was derived using a comparison of upper and lower of confidence interval boundaries at the 95% level of confidence. The results reveal that uncertainty in the key parameters had a more significant influence on equilibrium concentrations of the chemical in the bulk compartments of soil and sediment than on concentrations in the other two bulk compartments, various sub-compartments and the six predominant transfer fluxes.

One hundred and eighty eight surface soil samples were collected from the Tianjin area to study the contamination of DDT and its metabolites. Measurements were taken for p,p'-DDE, p,p'-DDD, p,p'-DDT, o,p'-DDE, o,p'-DDD and o,p'-DDT for all samples. The results indicated that p,p'-DDT and p,p'-DDE were the predominant contaminant compounds in the surface soil samples, with mean concentrations of 27.5 and 18.8 ng g(-1) respectively. No significant differences in DDT concentrations were found between the soils from wastewater treated irrigated areas and other areas, suggesting that wastewater irrigation is not an important source of DDT in the area. However, the spatial distribution of soil DDTs levels in the area did correlate well with early direct application rates of pesticides. In addition, both pH level and organic carbon content are also known factors affecting the level of DDT and its metabolites. Although it was assumed that the use of these chemicals was banned in the early 1980s, the current concentration levels appear to be too high to be mere residuals after 20 years degradation.

The complexation constants for copper associated with different natural organic ligands, including dissolved organic carbon (DOC) extracted from water, water soluble organic carbon (WSOC), fulvic acid (FA) and humic acid (HA) from soil, were determined and then compared based on discrete single site model. Both ion-selective electrode (ISE) and anodic stripping voltammetry were used to determine the content of free copper ions, while the relative number of complexation sites was estimated using a fluorescence quenching (FQ) at the same time. ISE proved to be the most applicable technique when the concentration of copper was above 10(-7) moll(-1). The logk values for two WSOC sample sites (Song Ziyuan and Xin Niangtan) were 4.64 and 4.66; higher than both the DOC and HA values yet lower than the FA values, which were unusually high due to unavoidable pollution from the cation exchange resin used during the purification process. Binding affinities between the copper ions and the organic ligands obtained from streams in Yong Wei (DOC) and Song Ziyuan (WSOC) were influenced by pH, ion strength, and reactant concentration. Values for logk increased with increases in pH (ion strength of 0.1 N). At pH 4, the logk values decreased with increases in the supporting electrolyte concentration and total copper ion additions.

This paper presents the system-level responses of experimental lake ecosystems to three chemical stresses (acidification, copper and pesticide contamination) using exergy and structural exergy as ecological indicators. The results indicate that the doses or toxicity of the three chemical stressors contributed to changes in both exergy and structural exergy. Remarkable changes in exergy and structural exergy occurred under acidic conditions and in the presence of Dursban, 24D-DMA, permethrin, bifenthrin, Carbaryl, TCP, PCP, trichlorethylene, benzene, and high doses of Cu, oil, and hexazinone. This seemed to indicate that the subject ecosystems were seriously contaminated by these chemical stressors. For low doses of Cu, oil, atrazine, HCBP, and hexazinone, exergy and structural exergy were either unchanged or only slightly changed, suggesting that the lake ecosystems were not significantly impacted by these chemical stressors. Discussion of the relationships between ecosystem-level changes and structural and functional changes in stressed lake ecosystems indicates that the above-mentioned ecosystem-level changes were in accordance with the changes in structure and function. The observed changes in exergy and structural exergy were also consistent with Odum's predictions of shortened food chains, reduced resource use efficiency, poor stability, low information, and high entropy in stressed aquatic ecosystems. The findings lead the authors to conclude that it is feasible for exergy and structural exergy to serve as ecological indicators when characterizing the system-level responses of experimental lake ecosystems to chemical stress. These results for experimental lake ecosystems would be extrapolated to actual lakes.

A bioconcentration factor (BCF) estimation model for a wide range of nonionic organic compounds was developed on the basis of molecular connectivity indices and polarity correction factors. The nonlinear topological modeling using polarity correction factors resulted in the best BCF estimation quality for all of the 239 compounds studied, with a mean absolute estimation error of 0.478 log units. Residual analysis indicated that the estimation errors came from many sources including BCF measurement, test species, and selection of descriptors. Statistical robustness of the developed model was validated by modified jackknifed tests where random deletion of a set of compounds and specific deletion of a class of compounds were both performed. Comparison between the MCI-based (molecular connectivity indices) model and a Kow-based (octanol/water partition coefficient) model revealed that the BCF estimation based on topological parameters was as good as that achieved by Kow.

A fragment constant method for prediction of fish bioconcentration factor (BCF) was established based on experimental BCF values for 80 non-polar chemicals from nine classes. The model was evaluated using coefficients of determination and mean residuals, which are 0.995 and 0.1836, respectively. Jackknife tests were applied to examine the robustness of the prediction model on a class-by-class basis.

The kinetics of the leaching process of Water Soluble Organic Carbon (WSOC) from an upland soil were studied in a column leaching experiment. The pattern of the leaching curve indicated multiphasic release kinetics. A conceptual model was proposed to divide capillary and gravitational pores. The translocation of organic carbon in soil during leaching occurs in four sequential steps. 1) degradation of insoluble organic carbon to form WSOC; 2) desorption into capillary pore water; 3) diffusion towards gravitation pore water; and 4) leaching by convection flow. The overall kinetics of the leaching process can be depicted using an equation with three additive terms for degradation, desorption/diffusion, and convection, respectively.

The relationship between bioconcentration factors and molecular connectivity indices was investigated. A regression model was developed using 80 measured BCFs of nonpolar organic pollutants. The five topological parameters used were 1 chi, 2 chi, 3 chi c, 0 chi v and 2 chi v. Modified jackknife tests were applied to examine the robustness of the model by repeatedly removing a set of or a class of compounds from the database. The model was compared with one using Kow as an independent parameter. The mean absolute errors for the 80 compounds studied were 0.288 and 0.302 log-unit for the two models, respectively.