Multivariate statistical study of heavy metal enrichment in sediments of the Pearl River Estuary

The concentrations and chemical partitioning of heavy metals in the sediment cores of the Pearl River Estuary were studied. Based on Pearson correlation coefficients and principal component analysis results, Al was selected as the concentration normalizer for Pb, while Fe was used as the normalizing element for Co, Cu, Ni and Zn. In each profile, sections with metal concentrations exceeding the upper 95% prediction interval of the linear regression model were regarded as metal enrichment layers. The heavy metal accumulation mainly occurred at sites in the western shallow water areas and east channel, which reflected the hydraulic conditions and influence from riparian anthropogenic activities. Heavy metals in the enrichment sections were evaluated by a sequential extraction method for possible chemical forms in sediments. Since the residual, Fe/Mn oxides and organic/sulfide fractions were dominant geochemical phases in the enriched sections, the bioavailability of heavy metals in sediments was generally low. The 206Pb/207Pb ratios in the metal-enriched sediment sections also revealed the influence of anthropogenic sources. The spatial distribution of cumulative heavy metals in the sediments suggested that the Zn and Cu mainly originated from point sources, while the Pb probably came from non-point sources in the estuary.     

Fate and assessment of persistent organic pollutants in water and sediment from Minjiang River Estuary,Southeast China

Persistent organochlorine compounds were analyzed in surface water, porewater and surficial sediment samples from Minjiang River Estuary, which is the first large river in Fujian Province, Southeast of China. The total concentrations of 18 organochlorine pesticides were 214.4-1819, 4541-13,699 ng/l, 28.79-52.07 ng/g in surface water, porewater and sediments (dry weight) respectively, and those of 21 polychlorinated biphenyls (PCBs) in the three phases were: 203.9-2473, 3192-10,855 ng/l, 15.14-57.93 ng/g respectively. The results showed that the concentrations of these selected organochlorine pesticides and PCBs in porewater were higher than those in surface water. It may be due to the fact that these organic hydrophobic pollutants tend to stay in the sediments, and then re-suspend from the sedimentary phase to the upper water. We have analyzed the distribution characteristics of individual organochlorine pesticide components and PCBs, and found that alpha-HCH, DDE, Heptachlor, Endosulfan II, Methoxychlor were the most common organochlorine pesticides contaminants. Considering the groups of HCHs (HCHs=alpha-HCH+beta-HCH+gamma-HCH+delta-HCH) and DDTs (DDTs=DDT+DDD+DDE), the predominance of beta-HCH, DDE in all water, porewater and sediment samples was clearly observed. This observation suggested that beta-HCH was resistant to biodegradation and the DDTs had been transformed to its metabolites, DDE and DDD, of which DDE that was more un-degradable. The PCB congeners containing 3-6 chlorines had the great preponderance in the three phase. These results were compared with those present in other estuaries and harbors. A risk assessment was evaluated for the persistent organic pollutants in the Minjiang River Estuary.     

Negative effects of humic acid addition on phytoremediation of pyrene-contaminated sediments by mangrove seedlings

Vegetated (with Kandelia candel seedlings) and non-vegetated mangrove microcosms were employed to remove pyrene from contaminated sediments, and the effects of adding 6.7% humic acid (HA) on such removal were investigated. At the end of 6-month treatment, residual pyrene concentrations in surface sediments (0-2 cm) of the contaminated microcosms reduced from an initial 5.82 to 0.63 microg g(-1) dw, and the reduction was less in HA amended microcosms with the residual pyrene concentration remained at 3.12 microg g(-1) dw. The pyrene removal percentages in microcosms with HA amendment were 29% for surface aerobic sediments and 41% for bottom (anaerobic) sediments, while the respective removal percentages in microcosms without HA amendment were 89% (surface sediments) and 53% (bottom sediments). Microcosms planted with K. candel seedlings had a significantly higher pyrene removal when compared to the non-vegetated ones, and the average removal percentages were 70.9% and 61.4%, respectively. However, when humic acid was added, no significant difference was found between vegetated and non-vegetated microcosms in pyrene removal, both had less than 40% removal, probably because plant growth in humic acid amended contaminated microcosms, in terms of total biomass, was reduced by 50%. Roots of K. candel could accumulate pyrene from contaminated microcosms, and pyrene concentrations in roots harvested from microcosms with and without humic acid addition were 6.01 and 3.46 microg g(-1) dw, respectively. These results suggest that the addition of HA to contaminated sediments decreased the mangrove microcosm's ability to remove pyrene as pyrene was more tightly bound to the organic matter and plant growth was reduced.     

Spatial and temporal organic and heavy metal pollution at Mai Po Marshes Nature Reserve,Hong Kong

An intensive monthly sampling of water and sediments from 12 sites over 8 months covering wet and dry seasons at Mai Po Marshes Nature Reserve was conducted during June 1997-February 1998. Major organic (C, N and P) and heavy metal pollutants (Cd, Cr, Cu, Ni, Pb, Zn) water and sediment samples were examined. The results showed that Mai Po Marshes were severely polluted by organic matter and heavy metals, and the water from Deep Bay appeared to be the source of pollution. Up to 13-55% chance that the sediments of Mai Po Marshes were classified as moderately to seriously metal contaminated materials, according to the guideline set by Hong Kong Government. Empirical models describing organic matter and heavy metal spatial and seasonal dynamics in the water and sediments were formulated, based on data analysis. During wet season (June-October), more than 58% variations of total P can be explained by ortho-P in water, while ammonia-N explained up to 90% variations of total Kjeldahl nitrogen in water. Throughout the whole sampling period (June-February), there were significant correlations (p<0.01) between total organic C in water. pH in the sediments and salinity in water appeared to be important factors determining heavy metal mobility in sediments, while potential metal release from the sediments is a concern when any oxidizing processes such as flooding or dredging are imposed on sediments.     

Boreal bog plants: nitrogen sources and uptake of recently deposited nitrogen

The main goals of this study were to determine the delta15N signature of quantitatively important boreal bog plants as basis for discussing their N sources, and to assess the effects of five different 3 year N treatments (i.e. 0, 5, 10, 20 and 40 kg N ha(-1) year(-1)) on the bog plants and surface peat at different depths (i.e. 0, 5, 10, 20 and 40 cm) by using 15N as tracer. Plants and peat were analyzed for N concentration, 15N natural abundance and 15N at.%. From the results we draw three main conclusions: First, the relative importance of different N sources is species-specific among bog plants. Second, an annual addition of 5 kg N ha(-1) year(-1) was sufficient to significantly increase the N concentration in Sphagnum mosses, liverworts and shallow rooted vascular plants, and an annual addition of 40 kg N ha(-1) year(-1) during 3 years was not sufficient to increase the N concentration in deep rooted plants, although the 15N content increased continuously, indicating a possible longer term effect. Third, an annual addition of 40 kg N ha(-1) year(-1) during 3 years increased the N content in surface peat at depths of 5 and 10 cm, but not at depths of 20 and 40 cm, indicating the capacity of the living Sphagnum mosses and the surface peat to take up deposited N, and thereby function as a filter.     

Chemical and biological characterization of non-extractable sulfonamide residues in soil

For sulfonamides, the formation of non-extractable residues has been identified by laboratory testing as the most relevant concentration determining process in manured soil. Therefore, the present study has been focused on the chemical and biological characterization of non-extractable residues of ¹⁴C-labeled sulfadiazine or sulfamethoxazole. In laboratory batch experiments, the test substances were spiked via standard solution or test slurry to microbially active soil samples. After incubation periods of up to 102 d, a sequential extraction technique was applied. Despite the exhaustive extraction procedure, sulfadiazine residues mainly remained non-extractable, indicating the high affinity to the soil matrix. The remobilization of non-extractable ¹⁴C-sulfadiazine residues was monitored in the activated sludge test and the Brassica rapa test. Only small amounts (<3%) were transferred into the extractable fractions and 0.1% was taken up by the plants. In the Lumbricus terrestris test A, the release of non-extractable ¹⁴C-sulfamethoxazole residues by the burrowing activity of the earthworms was investigated. The residues mainly remained non-extractable (96%). The L. terrestris test B was designed to study the immobilization of ¹⁴C-sulfamethoxazole in soil directly after the test slurry application. The mean uptake by earthworms was 1%. Extractable and non-extractable residues amounted to 5% and 93%, respectively. Consequently, the results of all tests confirmed the high affinity of the non-extractable sulfonamide residues to the soil matrix.     

Study of metabolites from the degradation of polycyclic aromatic hydrocarbons (PAHs) by bacterial consortium enriched from mangrove sediments

The PAH metabolites produced during degradation of fluorene, phenanthrene and pyrene by a bacterial consortium enriched from mangrove sediments were analyzed using the on-fiber silylation solid-phase microextraction (SPME) combining with gas chromatography–mass spectrometry (GC–MS) method. Seventeen metabolites at trace levels were identified in different PAH degradation cultures based on the full scan mass spectra. In fluorene degradation cultures, 1-, 2-, 3- and 9-hydroxyfluorene, fluorenone, and phthalic acid were detected. In phenanthrene and pyrene degradation cultures, various common metabolites such as phenanthrene and pyrene dihydrodiols, mono-hydroxy phenanthrene, dihydroxy pyrene, lactone and 4-hydroxyphenanthrene, methyl ester, and phthalic acid were found. The detection of various common and novel metabolites demonstrates that SPME combining with GC–MS is a quick and convenient method for identification as well as monitoring the real time changes of metabolite concentrations throughout the degradation processes. The knowledge of PAH metabolic pathways and kinetics within indigenous bacterial consortium enriched from mangrove sediments contributes to enhance the bioremediation efficiency of PAH in real environment.     

Status of trace elements in paddy soil and sediment in Taihu Lake region

Thirteen paddy soil profiles and river sediments which are sources of irrigation water were collected around the Taihu Lake, and the trace elements were estimated. The content of La and Ce in paddy soil and sediment were 39.3 and 68.6 mg/kg soil and 36.9 and 65.1 mg/kg soil, being within the range of background values. The values for Pb, Cu, Ni, Cr, Co, Mn, Zn, Se in paddy soil were 23.3, 27.8, 25.5, 63.5, 10.2, 386, 68.7 and 0.25 mg/kg soil respectively, all below the national permission level. There was a decline of Zn in paddy soil. Some of the river sediments were seriously polluted. The river in Yangjin site was most contaminated with 5.47 g Cu/kg and 7.4 g Zn/kg. The high concentration of Pb and Ni also was observed in this sediment. River in Weitang, Huashi, Xinzhuang and Meiyan were contaminated with Pb, Cu and Ni to some extent. Zn, Cu and Pb were the main pollutants in present experiment sites. The fast development of village/township industries have caused severe environmental pollution in the Taihu Lake region, especially irrigation river sediments. Se content in plant and seed was 0.04 and 0.03 mg/kg respectively, showed Se-deficiency in paddy soil in the Taihu Lake region.     

Rapid degradation of butachlor in wheat rhizosphere soil

The degradative characteristics of butachlor in non-rhizosphere, wheat rhizosphere, and inoculated rhizosphere soils were measured. The rate constants for the degradation of butachlor in non-rhizosphere, rhizosphere, and inoculated rhizosphere soils were measured to be 0.0385, 0.0902, 0.1091 at 1 mg/kg, 0.0348, 0.0629, 0.2355 at 10 mg/kg, and 0.0299, 0.0386, 0.0642 at 100 mg/kg, respectively. The corresponding half-lives for butachlor in the soils were calculated to be 18.0, 7.7, 6.3 days at 1 mg/kg, 19.9, 11.0, 2.9 days at 10 mg/kg, and 23.2, 18.0, 10.8 days at 100 mg/kg, respectively. The experimental results show that the degradation of butachlor can be enhanced greatly in wheat rhizosphere, and especially in the rhizosphere inoculated with the bacterial community designated HD which is capable of degrading butachlor. It could be concluded that rhizosphere soil inoculated with microorganisms-degrading target herbicides is a useful pathway to achieve rapid degradation of the herbicides in soil.     

Effects of EDTA and low molecular weight organic acids on soil solution properties of a heavy metal polluted soil

A pot experiment was conducted to study the effects of EDTA and low molecular weight organic acids (LMWOA) on the pH, total organic carbon (TOC) and heavy metals in the soil solution in the rhizosphere of Brassica juncea grown in a paddy soil contaminated with Cu, Zn, Pb and Cd. The results show that EDTA and LMWOA have no effect on the soil solution pH. EDTA addition significantly increased the TOC concentrations in the soil solution. The TOC concentrations in treatments with EDTA were significantly higher than those in treatments with LMWOA. Adding 3 mmol kg(-1) EDTA to the soil markedly increased the total concentrations of Cu, Zn, Pb and Cd in the soil solution. Compared to EDTA, LMWOA had a very small effect on the metal concentrations. Total concentrations in the soil solution followed the sequence: EDTA > citric acid (CA) approximately oxalic acid (OA) approximately malic acid (MA) for Cu and Pb; EDTA > MA > CA approximately OA for Zn; and EDTA > MA > CA > OA for Cd. The labile concentrations of Cu, Zn, Pb and Cd showed similar trends to the total concentrations.