Stable hydrogen,carbon and chlorine isotope measurements of selected chlorinated organic solvents

Stable hydrogen isotopes of two chlorinated solvents, trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA), provided by five different manufacturers, were determined and compared to their carbon and chlorine isotopic signatures. The isotope ratio for delta2H of different TCEs ranged between +466.9 per thousand and +681.9 per thousand, for delta13C between -31.57 per thousand and -27.37 per thousand, and for delta37Cl between -3.19 per thousand and +3.90 per thousand. In the case of the TCAs, the isotope ratio for delta2H ranged between -23.1 per thousand and +15.1 per thousand, for delta13C between -27.39 per thousand and -25.84 per thousand, and for delta37Cl between -3.54 per thousand and +1.39 per thousand. As well, a column experiment was carried out to dechlorinate tetrachloroethylene (PCE) to TCE using iron. The dechlorination products have completely different hydrogen isotope ratios than the manufactured TCEs. Compared to the positive values of delta2H in manufactured TCEs (between +466.9 per thousand and +681.9 per thousand), the dechlorinated products had a very depleted delta2H (less than -300 per thousand). This finding has strong implications for distinguishing dechlorination products (PCE to TCE) from manufactured TCE. In addition, the results of this study show the potential of combining 2H/1H analyses with 13C/12C and 37Cl/35Cl for isotopic fingerprinting applications in organic contaminant hydrogeology.     

The effects of soil amendments on heavy metal bioavailability in two contaminated Mediterranean soils

Two heavy metal contaminated calcareous soils from the Mediterranean region of Spain were studied. One soil, from the province of Murcia, was characterised by very high total levels of Pb (1572 mg kg(-1)) and Zn (2602 mg kg(-1)), whilst the second, from Valencia, had elevated concentrations of Cu (72 mg kg(-1)) and Pb (190 mg kg(-1)). The effects of two contrasting organic amendments (fresh manure and mature compost) and the chelate ethylenediaminetetraacetic acid (EDTA) on soil fractionation of Cu, Fe, Mn, Pb and Zn, their uptake by plants and plant growth were determined. For Murcia soil, Brassica juncea (L.) Czern. was grown first, followed by radish (Raphanus sativus L.). For Valencia soil, Beta maritima L. was followed by radish. Bioavailability of metals was expressed in terms of concentrations extractable with 0.1 M CaCl2 or diethylenetriaminepentaacetic acid (DTPA). In the Murcia soil, heavy metal bioavailability was decreased more greatly by manure than by the highly-humified compost. EDTA (2 mmol kg(-1) soil) had only a limited effect on metal uptake by plants. The metal-solubilising effect of EDTA was shorter-lived in the less contaminated, more highly calcareous Valencia soil. When correlation coefficients were calculated for plant tissue and bioavailable metals, the clearest relationships were for Beta maritima and radish.     

Effects of elevated soil copper on phenology,growth and reproduction of five ruderal plant species

The repeated use of copper (Cu) fungicides to control vine downy mildew, caused by Plasmopara viticola, has been responsible for the heavy increase of Cu concentration in the upper layers of vineyard soils. To determine the effects of elevated soil Cu on plant development, we created an artificial soil gradient with Cu enrichments ranging from 0 to 400 mg kg-1. On this gradient, and for five ruderal plant species commonly found in vineyards in southern France (Poa annua L., Dactylis glomerata L., Senecio vulgaris L., Hypochoeris radicata L., and Andryala integriflolia L.), we quantified survival, growth, and reproduction throughout one flowering season. High concentrations of Cu in the soil resulted in low survival, low total plant biomass, delay in flowering and fruiting, and low seed set. However, the effects differed among species. Furthermore, high soil Cu concentrations had contrasting effects on patterns of resource allocation depending on the plant species.     

Changes of copper speciation in maize rhizosphere soil

Chemical forms of copper in the rhizosphere and bulk soil of maize were investigated using rhizobox cultivation and sequential extraction techniques. The copper accumulations were also determined. The results demonstrated that there were continuous changes in copper fractionation within the maize rhizosphere. Initially, the amount of exchangeable copper increased before dropping below the initial level after 40 days or so. Carbonate associated copper followed a similar trend of change, but with a slower pace than the exchangeable copper. The increase in carbonate associated copper only become evident after 30 days, with the net loss occurring after 60 days. There were also initial increases in oxide bound copper as well as decreases in the organic matter associated copper, both followed by a turnover after 40-50 days. The accumulation of copper in the maize plant was found to be biomass dependent. The amount of accumulated copper absorbed in the plant material exceeded the initial quantity of the exchangeable copper in the soil, revealing a transformation from less bioavailable to more bioavailable fractions. During cultivation, decreases in redox potential and increases in pH, dissolved organic carbon (DOC), and microbial activity in the maize rhizosphere were observed. The change in copper speciation may result from root-induced changes in DOC, redox potential, and microbial activity in the rhizosphere.     

Trace metal behaviour in the Conwy estuary,North Wales

The distribution of trace metals Zn, Ni, Mn, Fe, Cu, Pb, Cd and Cr between suspended particulate matter (SPM) and water in the Conwy estuary, North Wales, has been studied in three surveys in 1998. Dissolved Cu and Mn showed some monthly variations. Most of the dissolved trace metals displayed a negative association with salinity, indicating rivers as a major source of inputs for them. Particulate Zn, Mn and Fe showed a decreasing concentration seaward, whilst the levels of Ni, Cu, Cr and Pb increased with salinity. SPM concentration was the most important variable significantly related to trace metal concentrations in SPM, with an inverse relationship between the two parameters. This was explained by the relative enrichment of trace metals in fine particles at low SPM concentrations and relative depletion of trace metals in coarse particles at high SPM concentrations. Particulate Zn, Mn and Pb were dominated by the fraction available to acetic acid (non-detrital), whilst particulate Ni, Fe and Cr were dominated by the fraction available to nitric acid (detrital). The partition coefficient of trace metals between SPM and water declined with increasing SPM concentration, consistent with the so-called "particle concentration effect". Such a phenomenon may be explained by the presence of fine particles (including colloids) enriched with trace metals at low SPM concentrations, and the salinity-induced desorption.     

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.     

Differences between weekday and weekend air pollutant levels in southern California

Ambient air quality data were analyzed to empirically evaluate the effects of reductions of volatile organic compounds (VOCs) and oxides of nitrogen (NOx) emissions on weekday and weekend levels of ozone (O3; 1991-1998) and particulate NO3- (1980-1999) in southern California. Despite significantly lower O3 precursor levels on weekends, 20 of 28 South Coast Air Basin (SoCAB) sites (28 of all 78 southern California sites) showed statistically significant higher mean O3 levels on Sundays than on weekdays (p < 0.01); 49 of the remaining 50 sites showed no significant differences between mean weekday and Sunday peak O3 levels. We also observed no statistically significant differences between mean weekday and weekend concentrations of particulate NO3- or nitric acid (HNO3, the precursor of particulate NO3-). Averaged over sites, the mean Sunday NOx and nonmethane hydrocarbon concentrations were 25-41% and 16-30% lower, respectively, than on weekdays. Site-to-site differences between weekend and weekday mean peak hourly O3 levels were related to whether O3 formation was limited by the availability of NOx. A thermodynamic equilibrium model predicts that particulate NO3- levels would decrease in response to a reduction of HNO3, and that particulate ammonium NO3- formation was not limited by the availability of ammonia. The similarity of mean weekday and weekend levels of NO3- therefore did not result from limitations on the formation of particulate NO3- from its precursor, HNO3.     

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.     

The role of humic substances in chromium sorption onto natural organic matter (peat)

To elucidate mechanisms of Cr³⁺ sorption onto the unaltered solid natural organic matter, the comparative studies of this ion binding from a solution at pH 4.0 onto three selected particle size fractions: 2000–1000 μm, 630–200 μm and 63–20 μm of markedly different HS content and structure, separated by a wet sieving from an overall sample of peat (Brushwood Peat Humus) were carried out. Comparable patterns of COOH groups and CEC_t confirmed that for cation exchange capacity were responsible mainly cations connected with COO⁻ functional groups. It was though found that aliphatic acids in the solid state did not take part in Cr³⁺ binding, thus the finest studied fraction 63–20 μm of the highest contents of functional groups showed the lowest sorption capacity for Cr³⁺, while similar patterns of sorbed Cr³⁺, soluble HS content and base CEC₀ indicated that these parameters were directly interrelated. The base ion exchange processes determined by CEC₀ (with Ca²⁺ as a predominant exchangeable cation) appeared to be not the major mechanisms responsible for Cr³⁺ sorption. For this metal, strong binding to insoluble large molecular weight organic pool two- to threefold prevailed over the ion exchange processes. Very low acid desorption indicated generally low mobility of Cr³⁺-organic compounds.     

Copper complexation by tannic acid in aqueous solution

The speciation of titrated copper in a dissolved tannic acid (TA) solution with an initial concentration of 4 mmol organic carbon (OC)/l was investigated in a nine-step titration experiment (Cu/OC molar ratio = 0.0030–0.0567). We differentiated between soluble and insoluble Cu species by 0.45 μm filtration. Measurements with a copper ion selective electrode (ISE) and diffusive gradients in thin films (DGT) were conducted to quantify unbound Cu(II) cations (‘free’ Cu) and labile soluble Cu complexes. For the DGT measurements, we used an APA hydrogel and a Chelex 100 chelating resin (Na form). Insoluble organic Cu complexes (>0.45 μm) was the dominant Cu species for Cu/OC = 0.0030–0.0567 with a maximum fraction of 0.96 of total Cu. At Cu/OC > 0.0100, Cu-catalysed degradation of aggregate structures resulted in a strong increase of free Cu and (labile) soluble Cu complexes with a maximum fraction of 0.28 and 0.32 of total Cu, respectively. Labile (i.e. DGT-detectable) soluble Cu complexes had a relatively high averaged diffusion coefficient (D) in the APA hydrogel (3.50 × 10⁻⁶– 5.58 × 10⁻⁶ cm² s⁻¹).