Spatial variation of heavy metals in surface sediments of Hong Kong mangrove swamps

The degree of heavy metal contamination in the fine-grained (<63 microm) and sand-sized (2 mm-63 microm) fractions of surface sediments in 18 different mangrove swamps (144 random samples) in Hong Kong was examined. Higher concentrations of heavy metals were found in the fine-grained than the sand-sized fractions of the sediment; however, the differences between these two fractions became less significant when the swamp was more contaminated. The principal component analyses show that the 18 mangrove swamps, according to the median concentrations of total heavy metals, were clustered into four groups. The first group included three mangrove swamps in Deep Bay region which are seriously contaminated, with heavy metal concentrations in sediments around 80 microg g(-1) Cu, 240 microg g(-1) Zn, 40 microg g(-1) Cr, 30 microg g(-1) Ni, 3 microg g(-1) Cd and 80 microg g(-1) Pb. The second cluster, made up of another four swamps distributed in different geographical locations (two in Sai Kung district and two in Tolo region), also had elevated levels of Cu, Pb, Ni and Cr in the sediments. Field observation reveals that these seven stands received industrial, livestock and domestic sewage as well as pollution from mariculture activities, suggesting that anthropogenic input is the main source of heavy metal contamination in Hong Kong mangroves. The sediments from other mangrove swamps were relatively uncontaminated.     

Modulation of steroidogenesis by coastal waters and sewage effluents of Hong Kong, China, using the H295R assay

BACKGROUND, AIM, AND SCOPE: The presence of a variety of pollutants in the aquatic environment that can potentially interfere with the production of sex steroid hormones in wildlife and humans has been of increasing concern. The aim of the present study was to investigate the effects of extracts from Hong Kong marine waters, and influents and effluents from wastewater treatment plants on steroidogenesis using the H295R cell bioassay. After exposing H295R cells to extracts of water, the expression of four steroidogenic genes and the production of three steroid hormones were measured. MATERIALS AND METHODS: Water samples were collected during the summer of 2005 from 24 coastal marine areas and from the influents and effluents of two major waste water treatment plants (WWTPs) in Hong Kong, China. Samples were extracted by solid phase extraction (SPE). H295R cells were exposed for 48 h to dilutions of these extracts. Modulations of the expression of the steroidogenic genes CYP19, CYP17, 3betaHSD2, and CYP11beta2 were determined by measuring mRNA concentrations by real-time polymerase chain reaction (Q-RT-PCR). Production of the hormones progesterone (P), estradiol (E2), and testosterone (T) was quantified using enzyme linked immunosorbent assays (ELISA). RESULTS: Extracts from samples collected in two fish culture areas inhibited growth and proliferation of H295R cells at concentrations greater or equal to 10(5) L equivalents. The cells were exposed to the equivalent concentration of active substances in 10,000 L of water. Thus, to observe the same level of effect as observed in vitro on aquatic organisms would require a bioaccumulation factor of this same magnitude. None of the other 22 marine samples affected growth of the cells at any dilution tested. Twelve of the marine water samples completely inhibited the expression of CYP19 without affecting E2 production; inhibition of CYP17 expression was observed only in one of the samples while expression of CYP11beta2 was induced as much as five- and ninefold after exposure of cells to extracts from two locations. The expression of the progesterone gene 3betaHSD2 was not affected by any of the samples; only one sample induced approximately fourfold the production of E2. Although more than twofold inductions were observed for P and T production, none of these values were statistically significant to conclude effects on the production of these two hormones. While influents from WWTPs did not affect gene expression, an approximately 30% inhibition in the production of E2 and a 40% increase in P occurred for the exposure with influents from the Sha Tin and Stonecutters WWTPs, respectively. Effluents from WWTPs did not affect the production of any of the studied hormones, but a decrement in the expression of the aldosterone gene CYP11beta2 was observed for the Sha Tin WWTP exposure. No direct correlation could be established between gene expression and hormone production. DISCUSSION: Observed cytotoxicity in the two samples from fish culture areas suggest the presence of toxic compounds; chemical analysis is required for their full identification. Although effluents from WWTPs did not affect hormone production, other types of endocrine activity such as receptor-mediated effects cannot be ruled out. Interactions due to the complexity of the samples and alternative steroidogenic pathways might explain the lack of correlation between gene expression and hormone production results. CONCLUSIONS: Changes observed in gene expression and hormone production suggest the presence in Hong Kong coastal waters of pollutants with endocrine disruption potential and others of significant toxic effects. The aromatase and aldosterone genes seem to be the most affected by the exposures, while E2 and P are the hormones with more significant changes observed. Results also suggest effectiveness in the removing of compounds with endocrine activity by the WWTPs studied, as effluent samples did not significantly affect hormone production. The H295R cell showed to be a valuable toll in the battery required for the analysis of endocrine disrupting activities of complex environmental samples. RECOMMENDATIONS AND PERSPECTIVES: Due to the intrinsic complexity of environmental samples, a combination of analytical tools is required to realistically assess environmental conditions, especially in aquatic systems. In the evaluation of endocrine disrupting activities, the H295R cell bioassay should be used in combination with other genomic, biological, chemical, and hydrological tests to establish viable modes for endocrine disruption and identify compounds responsible for the observed effects.     

Temporal and spatial patterns of micropollutants in urban receiving waters

Based on a monitoring program over the course of a year, we characterize the temporal and spatial distribution of selected micropollutants in an urban watershed within the city of Leipzig, Germany. Micropollutants revealed a ubiquitous presence in untreated and treated wastewater, surface water and groundwater. The loads of 4-nonylphenol in the effluents of the municipal wastewater treatment plant followed a seasonal trend, whereas the loads of all other micropollutants were highly variable and not correlated to seasons. In the surface water, load seasonality of caffeine, galaxolide and tonalide resulted from a rapid removal with increased water temperature. The loads of 4-nonylphenol and of caffeine in the colder months increased when rainfall occurred. In the groundwater, complex spatial and temporal patterns were apparent and were related to varying input, retardation and removal processes. As a consequence, an assessment of micropollutants in urban waters should consider different micropollutants' temporal and spatial variability.     

Trace metals in mussels from mariculture zones, Hong Kong

In 1997, concentrations of cadmium (Cd), chromium (Cr), copper (Cu), lead (Pb) and nickel (Ni) were analysed in green-lipped mussels (Perna viridis) from three mariculture zones located in the north-east (Kat O), south (Lo Tik Wan) and to the west (Ma Wan) of Hong Kong. Spatial differences in the concentration of metals were found, chromium and copper were higher at Ma Wan and Lo Tik Wan compared to Kat O in the north-east. In contrast, the highest levels of lead (mean = 4.37 microg/g dry wt) were recorded at Kat O. There were no differences in the level of nickel between the study sites. A comparison of the metal concentrations in mussels with the results of a previous study seven years before, in 1990, showed a twofold increase in the mean levels of cadmium for all three sites. However, levels of the other metals in 1997 were lower by 12-32% for chromium, 32-39% for copper and 24-25% for nickel. The greatest reductions were recorded for lead: Kat O (39%), Ma Wan (51%) and Lo Tik Wan (75%). This may be related to the introduction of lead-free petrol in 1991. Despite the apparent reduction in some heavy metal bioaccumulation between 1990 and 1997, from a public health risk perspective, the data suggest a continued need for monitoring of heavy metals in mussels from mariculture zones.     

In-stack emissions of heavy metals estimated by moss biomonitoring method and snow-pack analysis

Data from the chemical analysis of moss growing close to a thermal power station and snowpack have been used for the estimation of heavy metal deposition close to the point pollution sources. A semi-empirical model was proposed to describe atmospheric trace metal deposition close to the point pollution source. Model parameters were derived from experimental data, and nickel and vanadium quantities, washed out with snow and rain, were calculated. Using long-term meteorological observation data of rain and snow duration and metal uptake efficiencies in moss, the average emission rates of vanadium and nickel from the stack were calculated. The coincidence between data from emission inventory and model results was within 25%. It was estimated that in the vicinity of pollution source (within 30 km) about 15% out of total emitted metals were washed out by rain and snow events. Metal concentrations in the environment become indistinguishable from the background at a distance of about 20 km from the stack.     

Interspecific variation in heavy metal body concentrations in Hong Kong marine invertebrates

Accumulated body concentrations of cadmium, copper and zinc were investigated in 19 species of intertidal invertebrates (the barnacles Tetraclita squamosa, Capitulum mitella, Balanus amphitrite, Megabalanus volcano, the bivalves Saccostrea cucullata, Septifer virgatus and Brachidontes atratus, the chiton Acanthopleura japonica and the gastropods Cellana grata, Cellana toreuma, Patelloida saccharina, Patelloida pygmaea, Siphonaria japonica, Tegula argyrostoma, Lunella coronata, Monodonta labio, Nerita albicilla, Thais clavigera and Thais luteostoma) collected from a relatively unpolluted area in Hong Kong, i.e. two shores within the Cape d'Aguilar Marine Reserve. In general body metal concentrations could be explained by the accumulation strategy of the analysed organism and by physiological requirements for the essential metals, i.e. copper and zinc. Zinc concentrations were, therefore, greatest in the barnacles and the oyster S. cucullata. Copper concentrations were greatest in those gastropods containing the respiratory pigment haemocyanin and in S. cucullata. One species collected from the sheltered shore, i.e. T. luteostoma, had much higher copper body concentrations compared with exposed shore conspecifics and this may be attributed to a diet that was dominated by oysters, which have high copper body concentrations. In contrast to both copper and zinc, cadmium body concentrations showed little interspecific variation.     

Active biomonitoring of heavy metal pollution using Rosa rugosa plants

The purpose of this work was to evaluate the quality of a rural area near Faenza (Italy) by using an active biomonitoring approach, i.e., by placing homogeneous individuals of the perennial shrub Rosa rugosa in different sites throughout the area. Further sites, within the city or its environs, were used for comparison. Soil and leaves of R. rugosa were analyzed for their heavy metal content. The total heavy metal pattern of leaves closely paralleled the pattern registered in soil, with the highest content (both in total and assimilable forms) at the site in the urban area, which is exposed to heavy traffic. Pollen quality (abortiveness and viability) was also tested as a potential indicator of pollution. Pollen abortiveness was strictly related to Pb levels in leaves, while viability was inversely related to leaf Cr content. Our results suggest that R. rugosa has the potential to be a good biomonitoring system.     

Analyses of airborne Be concentrations in Hong Kong using back-trajectories

A total of 71 air samples were collected in Hong Kong area from November 2001 to February 2003 using a high-volume air sampler and a high-volume cascade impactor with five atmospheric pressure stages. The ⁷Be radioactivity on each stage was measured using a high-efficiency germanium gamma-ray spectrometer. From the radioactivity of stages, the total airborne ⁷Be radioactivity was determined. The activity median aerodynamic diameter (AMAD) of ⁷Be-associated atmospheric aerosols was found to be 0.22–1.11 μm and the geometric standard deviation (GSD) was found to be 1.2–10.5. With the assumed mean growth rate (MGR) of atmospheric aerosols of 0.004–0.005 μm h⁻¹ and the size of Aitken nuclei of 0.015 μm, the residence times of ⁷Be-associated atmospheric aerosols were also found from the AMAD.Three-dimensional 4-day back-trajectories were obtained using the HYSPLIT model from NOAA Air Resources Laboratory. These trajectories were used with the measured ⁷Be radioactivity to construct regional ⁷Be intensity fields for four different altitude levels (less than 1000, 1000–2000, 2000–3000 and above 3000 m) with a Geographic Information System (GIS). Low ⁷Be intensities were found to have advected from low altitudes (less than 1000 m) and oceanic areas. The ⁷Be intensities increased for the higher intensity field layers.By comparing the time taken for air masses to come from the ⁷Be source to Hong Kong and the residence time determined from the AMAD of ⁷Be-associated atmospheric aerosols, good agreement was found if the mean growth rate of 0.005 μm h⁻¹ for atmospheric aerosols was used, and the use of back-trajectories was shown to be satisfactory even up to about 6.5 d. By using the residence time with a MGR of 0.005 μm h⁻¹, the ⁷Be source was found to be relatively well confined in the areas of Mongolia and southeastern Siberia, which further supported that the association of ⁷Be source with the Siberian anticyclone.     

Temporal and spatial variation of sulfur-gas-transfer between coastal marine sediments and the atmosphere

The spatial and temporal variability of sulfur gas fluxes (H₂S, COS, CH₃SH, DMS, and CS₂) at the sediment–air interface were studied in the intertidal Wadden Sea area of Sylt-Rømø (Germany/Denmark) during eight measuring campaigns between June 1991 and September 1994. Measurements were performed mainly at four sites in a sheltered intertidal bay of approximately 6 km² (Königshafen) and discontinuously in a wider range of the 400 km² Sylt-Rømø tidal flat area. In situ fluxes of the S-gases were determined by a dynamic chamber technique focusing on dry sediment periods. Additional experiments were conducted in order to determine changes in S-gas concentrations in the sediment between the surface and 70 cm depth.In most cases H₂S was the dominant S-gas emitted from the sediment to the atmosphere, contributing up to 70% of the total S-emission at this interface. Mean H₂S emission rates ranged between 0.07 and 9.95 μg S m^-2 h^-1. Both emission rates and relative contribution of H₂S were lowest from fine sand and highest from muddy sites. Diurnal variation of H₂S emission was evident in summer and fall with up to 10-fold higher rates during night than during the day. Distinct seasonal variation of H₂S-transfer between the sediment and the atmosphere was observed with higher emission rates in the summer than in spring or fall. The emission of H₂S to the atmosphere was smaller by a factor of 1600–26 000 than the H₂S produced from sulfate reduction. Apparently, the efficiency by which H₂S produced in the sediment is retained and reoxidized by biogeochemical sediment processes is extremely high. Carbonyl sulfide (COS) was emitted with relatively constant rates in space and time with mean flux rates ranging between 0.24 and 2.0 μg S m^-2 h^-1. Carbon disulfide emission rates were comparable to those of COS and varied between 0.3 and 2.23 μg S m^-2 h^-1. DMS played a minor role in the S-gas transfer from uncovered sediment areas contributing between 3.1 and 23% to total S-emission from the sediment to the atmosphere.     

A comparison of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) for monitoring chlorinated trace organic contaminants in Hong Kong coastal waters.

A comparison of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) was carried out at five sites, representing a gradient of contaminant concentrations, in Hong Kong coastal waters. Mussels, originally collected from a “clean” location, were deployed along with SPMDs at each site for 30 days. Analyses for chlorinated pesticides and polychlorinated biphenyls (PCBs) indicated that SPMDs have potential as monitoring tools, and to some extent can overcome the problems associated with mussels, such as natural variability, differing age, sex, and physical condition. However, in most cases, SPMDs failed to rank the sites in the same order as mussels in terms of contaminant concentrations. Nonetheless, in localities where mussels cannot survive – as shown at Kwun Tong in the present experiment – SPMDs may be valuable in providing an indication of potentially bio-available lipophilic pollutants.     

A comparison of polycyclic aromatic hydrocarbon and petroleum hydrocarbon uptake by mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) in Hong Kong coastal waters

The ability of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) to accumulate polycyclic aromatic hydrocarbons (PAHs) and petroleum hydrocarbons (PHCs) from five sites in Hong Kong's coastal waters was compared. Mussels consistently had higher levels of contaminants, but their utility was limited at one highly polluted site due to mortality. Mussels and SPMDs ranked sites differently in terms of individual contaminant levels. Although SPMDs overcome many of the disadvantages of using living organisms to measure contaminants in marine waters, they cannot be used as "mimics" due to different PAH and PHC accumulation patterns.     

Synoptic conditions associated with high carbon monoxide episodes at a coastal station in Hong Kong

The effect of different synoptic environments and the associated meteorological conditions on the transport of CO to a coastal station located at the southeastern tip of Hong Kong are examined. Based on the 1994 data, we found that the appearance of a Siberia high pressure, the passage of a cold front, the passage of a trough, and the existence of a tropical cyclone to the east to southeast of Hong Kong frequently gave rise to continental outflow from a northeasterly to a northwesterly direction. This continental airstream, which is highly contaminated with anthropogenic air pollutants, raised the CO concentration at the station to a level significantly above the oceanic value (measured to be around 81 pbbv under persistent maritime flow conditions). We also identified 20 high CO episodes in which the CO concentration of at least two consecutive hourly means in a given month exceeded two standard deviations from the monthly mean. All these episodes were directly associated with one of the above four types of synoptic environments with the winds being moderate to light northwesterly to northeasterly.     

A comparison of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) for monitoring chlorinated trace organic contaminants in Hong Kong coastal waters

A comparison of mussels (Perna viridis) and semi-permeable membrane devices (SPMDs) was carried out at five sites, representing a gradient of contaminant concentrations, in Hong Kong coastal waters. Mussels, originally collected from a “clean” location, were deployed along with SPMDs at each site for 30 days. Analyses for chlorinated pesticides and polychlorinated biphenyls (PCBs) indicated that SPMDs have potential as monitoring tools, and to some extent can overcome the problems associated with mussels, such as natural variability, differing age, sex, and physical condition. However, in most cases, SPMDs failed to rank the sites in the same order as mussels in terms of contaminant concentrations. Nonetheless, in localities where mussels cannot survive – as shown at Kwun Tong in the present experiment – SPMDs may be valuable in providing an indication of potentially bio-available lipophilic pollutants.     

半焦吸附养殖废水中的重金属

采用生物质半焦作为吸附剂处理养殖废水中的重金属,并对半焦吸附重金属的吸附容量及吸附效率进行了分析和评估。实验结果表明,生物质半焦对养殖废水中Cu、Zn、Pb和Cd 4种重金属具有较好的吸附效果,吸附容量分别为22.4、19.03、17.30和16.94 mg/g,且吸附率均达到70%以上,氮磷的影响吸附不超过30%。重金属离子在半焦表面上的吸附过程符合Langmuir等温吸附模型,且主要为单分子层表面吸附。由此生物质半焦作为廉价高效的吸附剂处理养殖废水中重金属技术上可行,为养殖废水中重金属吸附研究及生物质半焦资源化利用提供新途径。     

Seasonal and spatial variation of solvent extractable organic compounds in fine suspended particulate matter in Hong Kong

The results of a 12-month study of more than 100 solvent extractable organic compounds (SEOC) in particulate matter (PM) less than or equal to 2.5 microm (PM2.5) collected at three air monitoring stations located at roadside, urban, and rural sites in Hong Kong are reported. The total yield of SEOC that accounts for approximately 8-18% of organic carbon (OC) determined by a thermal optical transmittance method was 125-2060 ng/m3, which included 14.6-128 ng/m3 resolved aliphatic hydrocarbons, 39.4-1380 ng/m3 unresolved complex mixtures, 0.6-17.2 ng/m3 polycyclic aromatic hydrocarbons, 41.6-520 ng/m3 fatty acids, and < 0.1-12.1 ng/m3 alkanols. Distinct seasonal variations (summer/winter differences) were observed with higher concentrations of the total and each class of SEOC in the winter and lower concentrations in the summer. Spatial variations are also obvious, with the roadside samples having the highest concentrations of SEOC and the rural samples having the lowest concentrations in all seasons. Characteristic ratios of petroleum hydrocarbons, such as carbon preference index, unresolved to resolved components, and carbon number with maximum concentration, suggest that PM2.5 carbon in Hong Kong originates from both biogenic and anthropogenic sources. The proportion of SEOC in PM2.5 from anthropogenic sources is estimated.     

The influence of mariculture on mercury distribution in sediments and fish around Hong Kong and adjacent mainland China waters

To study the influence of mariculture on mercury (Hg) speciation and distribution in sediments and cultured fish around Hong Kong and adjacent mainland China waters, sediment samples were collected from six mariculture sites and the corresponding reference sites, 200-300 m away from the mariculture sites. Mariculture activities increased total mercury, organic matter, carbon, nitrogen and sulfur concentrations in the surface sediments underneath mariculture sites, possibly due to the accumulation of unconsumed fish feed and fish excretion. However, methylmercury (MeHg) concentrations and the ratio of MeHg to THg (% MeHg) in sediments underneath mariculture sites were lower than the corresponding reference sites. The % MeHg in sediments was negatively correlated (r = −0.579, p < 0.05) with organic matter (OM) content among all sites, indicating that OM may have inhibited Hg methylation in surface sediments. Three mariculture fish species were collected from each mariculture site, including red snapper (Lutjanus campechanus), orange-spotted grouper (Epinephelus coioides) and snubnose pompano (Trachinotus blochii). The average MeHg concentration in fish muscle was 75 μg kg⁻¹ (wet weight), and the dietary intake of MeHg through fish consumption for Hong Kong residents was 0.37 μg kg⁻¹ week⁻¹, which was lower than the corresponding WHO limits (500 μg kg⁻¹ and 1.6 μg kg⁻¹ week⁻¹).     

Characterization and spatial distribution of heavy metals in sediment from Cedar and Ortega rivers subbasin

The Cedar and Ortega rivers subbasin is a complex environment where both natural and anthropogenic processes influence the characteristics and distributions of sediments and contaminants, which in turn is of importance for maintenance, dredging and pollution control. This study investigated the characteristics and spatial distribution of heavy metals, including lead (Pb), copper (Cu), zinc (Zn) and cadmium (Cd), from sediments in the subbasin using field measurements and three-dimensional kriging estimates. Sediment samples collected from three sampling depth intervals (i.e., 0-0.10, 0.11-0.56 and 0.57-1.88 m) in 58 locations showed that concentrations of Pb ranged from 4.47 to 420.00 mg/kg dry weight, Cu from 2.30 to 107.00 mg/kg dry weight, Zn from 9.75 to 2,050.00 mg/kg dry weight and Cd from 0.07 to 3.83 mg/kg dry weight. Kriging estimates showed that Pb, Cu and Cd concentrations decreased significantly from the sediment depth of 0.10 to 1.5 m, whereas Zn concentrations were still enriched at 1.5 m. It further revealed that the Cedar River area was a potential source area since it was more contaminated than the rest of the subbasin. Comparison of aluminum (Al)-normalized metal concentrations indicated that most of the metals within the top two intervals (0-0.56 m) had concentrations exceeding the background levels by factors of 2-10. A three-dimensional view of the metal contamination plumes showed that all of the heavy metals, with concentrations exceeding the threshold effect level (TEL) that could pose a threat to the health of aquatic organisms, were primarily located above the sediment depth of 1.5 m.     

Seasonal distribution and contamination levels of total PHCs, PAHs and heavy metals in coastal waters of the Alang-Sosiya ship scrapping yard, Gulf of Cambay, India

Alang-Sosiya situated on the Gulf of Cambay is one of the largest ship breaking yard in the world. The seasonal distribution and contamination levels of dissolved and/or dispersed total petroleum hydrocarbons (PHCs), total polycyclic aromatic hydrocarbons (PAHs) and heavy metals in seawater during high tide are investigated. The concentrations of petroleum hydrocarbons and heavy metals are higher in the winter than in the monsoon and summer. The concentrations of total PHCs and PAHs are about three times higher in the winter and two times in the monsoon or summer at Along-Sosiya and about twice in all seasons at two stations one on either side 5 km away from it as compared to the reference station at Mahuva, 60 km away towards the south. Further, the levels of PHCs are correlated with salinity and compared with those of other regions. The concentration of all metals is the highest in the winter season followed by the monsoon and summer. We carried out the quantitative analysis of the possible relationships among 13 variables such as Al, Fe, Pb, Mn, Cu, Zn, Cd, Cr, Co, pH, NO3-, NO2 and PO4(3-).     

Mobility of heavy metals from tailings to stream waters in a mining activity contaminated site

In this paper the results of a recent characterization of Rio Piscinas (SW of Sardinia, Italy) hydrological basin are reported. In such area (about 50 km2), previous mining activities caused a serious heavy metal contamination of surface waters, groundwater, soils and biota. Acid mine drainage phenomena were observed in the area. The main sources of contamination are the tailings stored in mine tunnels and abandoned along fluvial banks. A methodological approach was adopted in order to identify relations between tailings and water contamination. Representative samples of tailings and stream sediments samples were collected. XRD analyses were performed for mineralogical characterization, while acid digestion was carried out for determining metal contents. Batch sequential leaching tests were performed in order to assess metal mobility. Also groundwater and stream water were sampled in specific locations and suitably characterized. All information collected allowed the understanding of the effect of tailings on water contamination, thus contributing to the qualitative prediction of pollution evolution on the basis of metal mobility. Finally, a potential remediation strategy of stream water is proposed.