Predictions of nitrate diffusion in sediment using horizontal attenuated total reflection (HATR) by Fourier transform infrared (FTIR) spectrometry

Using a novel and simple method based on horizontal attenuated total reflection (HATR) by Fourier transform infrared (FTIR) spectrometry, the effective diffusion coefficient, De, of nitrate in a contaminated anthropogenic sediment was estimated as 7.34 x 10(-6)cm2 s(-1). This method, which requires as little as 1 mL of sediment sample, was able to measure the De of a chemical species with a reproducibility of +/-3% in about 5h. Based on this De and a pre-determined nitrate reduction rate, the profiles of nitrate concentration in two sediment columns were satisfactorily predicted from a mathematical model. Results showed that the profile in this aged sediment depended mainly on the diffusion of nitrate and, only to a much lesser degree, the rate of nitrate reduction. Measurements in 55 anthropogenic sediment samples collected from five locations and various depths of a contaminated site further showed that the De of nitrate increased linearly with the water content of the sediment, but decreased with the sediment density. The technique demonstrated in this study shall be applicable for the risk assessment of toxic pollutants in contaminated sediments, and for planning the spatial and time intervals of nitrate injection strategy in bioremediation.     

Review of toxicity test results submitted in support of pesticide tolerance petitions.

A long term-low level exposure (LLE) experiment was conducted on rats to determine the metabolic patterns for realistic environmental dietary levels of cadmium. Male rats fed with 61 ppb of cadmium ad libitum, 50 labelled with ¹⁰⁹Cd radiotracer as cadmium chloride via drinking mineral water and 11 unlabelled via food for 2 years. The diet was characterized in its metal content by neutron activation analysis to obtain the total dietary intake of different elements.The kidney was found to be the tissue with the major concentration of cadmium which accumulated continuously during the experiment.The variation of the accumulation pattern of Cd concentration in the liver and intestine indicated an initial rapid increase of Cd during the first 100 days. After this period an apparent equilibrium was attained in both these tissues until the end of the study.The intracellular distribution of cadmium in kidneys, liver, intestine and pancreas were similar, the cytosol fractions containing about 80% of the cellular cadmium. Dialysis experiments indicated that significant amounts of cadmium were able to be associated with cellular organelles, the mitochondria representing the most important organelle capable of binding cadmium.The cytoplasmatic Cd-profiles obtained at various stages of the experiment showed that the metal was only bound to a low-molecular-weight component, cadmium-binding protein (CdBP), which represents the specific cellular-binding component for cadmium under the long term-low level exposure (LLE) conditions.No significant variations in the concentrations of the elements in different organs were observed in animals supplemented with ¹⁰⁹Cd in respect to ¹⁰⁹Cd untreated controls.     

Effect of surfactants on the determination of aluminium in waters

Eleven surfactants representing pure cationic, anionic and nonionic detergents, four commercial detergents, sodium pyrophosphate, sodium tripolyphosphate, a soap and nitrilotriacetic acid (NTA) were investigated for their effect on the determination of aluminium in water using the eriochrome cyanine R, ferron-orthophenanthroline and chrome azurol S methods. Cationic, anionic and nonionic detergents at concentrations up to 2, 100 and 1000 mg l⁻¹, respectively, did not interfere. Sodium tripolyphosphate interfered badly above 1.0 mg l⁻¹, and therefore the interference by formulated detergents containing tripolyphosphate was serious. Concentrations of NTA, soap and sodium pyrophosphate had to be below 0.5, 10 and 20 mg l⁻¹, respectively, to limit the error to 5%.     

Formation of alkylated aromatic acids in groundwater by anaerobic degradation of alkylbenzenes

Evidence for the presence of previously unreported alkylated aromatic acids in anaerobic groundwater samples from a jet fuel-contaminated site is presented. The redox conditions are dominated by sulfate reduction. A gas chromatography/mass spectrometry screening showed a composition of aromatic hydrocarbons ranging from BTEX (C(0)-C(2)-substituted benzenes) up to C(7)-benzenes. Known metabolites like methylbenzoates (C(1)-BA), C(2)-BA, C(3)-BA as well as methylbenzylsuccinates (C(1)-BSA) were detected. Additionally, previously unreported metabolites of higher alkylated benzenes have been identified in the extracts: those are C(2)-BSA to C(5)-BSA as well as C(4)-BA to C(6)-BA, which were detected in the microg/l-concentration range. The formation of C(1)- and C(2)-BSA as well as the C(1)- and C(2)-BA can be linked to structurally corresponding parent contaminants like the xylene isomers and the trimethylbenzene isomers. The C(3)-BSA and C(3)-BA represent metabolites of C(4)-benzenes. The occurrence of C(4)-C(5)-BSA and C(4)-C(6)-BA is attributed to C(5)-C(7)-benzenes acting as parent compounds. The concentration of total aromatic contaminants decreased along the plume centre line. In contrast, benzoates and benzylsuccinates (BA and BSA) showed constant concentrations over a distance of 84 m. BA concentrations were up to 162 times higher compared to BSA, as indicated by the ratio f(BA/BSA). A pronounced transient behaviour of BSA or an overall persistent behaviour of BA can explain this. Hence, along the plume centre line, f(BA/BSA) was constant over a distance of 128 m. The degradation products detected in a monitoring well are not necessarily tied to contaminants detected in that well. Therefore, the metabolite plume is partly located in front of the contaminant plume, but does not significantly migrate downstream the plume toe.     

Shifting balances in U.S. metropolitan and nonmetropolitan area growth

"This paper assesses some of the recent attempts to explain the perceived growth reversal between metropolitan and nonmetropolitan areas in the United States during the 1970s. The paper argues that the reversal in population trends was not a one-time, radical shift in settlement trends, but rather the result of more continuous underlying industrial trends. Indeed, since 1979, population growth has again become faster in metropolitan than nonmetropolitan areas." The paper includes three sections. Regional and area population and industrial earnings growth patterns are first summarized for the 1960s, 1970s, and 1980s. Theories of polarization and polar reversal are then evaluated and found to be inadequate. Finally, a reconstruction of the neoclassical model is proposed.     

Reaction processes effecting the analysis of chloroform by direct aqueous injection gas chromatography

Several important reaction processes which influence the analysis of chloroform by direct aqueous injection (DAI) gas chromatography have been identified through an investigation of the chlorination reactions of humic acid and a series of simple polyhydroxyaromatic and diketone model compounds in dilute solution. The reaction of chlorine with each substrate system was studied over the pH range 2–12. Gas chromatographic analysis by the DAI and organic solvent liquid-liquid extraction (LLE) procedures gave different measurements for the yield of CHCl₃ depending on the pH of the reaction solution and the chemical structure of the substrate. Under acidic and neutral conditions, a variety of trichloromethyl-substituted intermediates were identified at high concentrations in addition to chloroform by GC/MS. Chloral hydrate, trichloroacetic acid, pentachloroacetone and hexachloroacetone undergo hydrolysis and/or decarboxylation to form CHCl₃ at the high injection port temperatures employed in aqueous injection GC analysis. The results obtained in the current study indicate that the decomposition of these and structurally-related species accounts for differences previously observed upon application of the DAI and either the LLE or purge-and-trap techniques for the determination of CHCl₃ in chlorinated natural waters.     

Radon and 'King Solomon's Miners': Faynan Orefield, Jordanian Desert

Concentrations of 222Rn were measured in ancient copper mines which exploited the Faynan Orefield in the South-Western Jordanian Desert. The concentrations of radon gas detected indicate that the ancient metal workers would have been exposed to a significant health risk and indicate that any future attempt to exploit the copper ores must deal with the hazard identified. Seasonal variations in radon concentrations are noted and these are linked to the ventilation of the mines. These modern data are used to explore the differential exposure to radon and the health of ancient mining communities.     

Arsenic and heavy metals in soils associated with regional geochemical anomalies in South-West England

Regional geochemical maps have shown extensive anomalies of arsenic, copper and other heavy metals in those parts of South-West England associated with mineralised zones around the granite intrusion. Studies in the vicinity of the River Tamar and of the metamorphic aureole around Dartmoor have confirmed significantly higher concentrations of arsenic and heavy metals in soils contaminated by mining, smelting and mineralisation compared with those from nearby control areas. Arsenic and copper show the greatest degree of enhancement ranging up to 900 ppm As and 2000 ppm Cu in both alluvial and upland topsoils within the Tamar area. Preliminary analyses indicate that the trace metal content of pasture herbage-reflects in part the degree of soil contamination. Maximum concentrations of 35 ppm As and 22 ppm Cu in autumn sampled herbage were found at contaminated sites compared with mean values of less than 0.5 ppm As and 8 ppm Cu in control areas. Geochemical reconnaissance surveys based on stream sediment sampling provide a useful indication of areas wherein widescale soil contamination may occur.     

Influences of iron, manganese, and dissolved organic carbon on the hypolimnetic cycling of amended mercury

The biogeochemical cycling of iron, manganese, sulfide, and dissolved organic carbon were investigated to provide information on the transport and removal processes that control the bioavailability of isotopic mercury amended to a lake. Lake profiles showed a similar trend of hypolimnetic enrichment of Fe, Mn, DOC, sulfide, and the lake spike ((202)Hg, purity 90.8%) and ambient of pools of total mercury (HgT) and methylmercury (MeHg). Hypolimnetic enrichment of Fe and Mn indicated that reductive mobilization occurred primarily at the sediment-water interface and that Fe and Mn oxides were abundant within the sediments prior to the onset of anoxia. A strong relationship (r(2)=0.986, n=15, p<0.001) between filterable Fe and Mn indicated that reduction of Fe and Mn hydrous oxides in the sediments is a common in-lake source of Fe(II) and Mn(II) to the hypolimnion and that a consistent Mn:Fe mass ratio of 0.05 exists in the lake. A strong linear relationship of both the filterable [Fe] (r(2)=0.966, n=15, p<0.001) and [Mn] (r(2)=0.964, n=15, p<0.001) to [DOC] indicated a close linkage of the cycles of Fe and Mn to DOC. Persistence of iron oxides in anoxic environments suggested that DOC was being co-precipitated with Fe oxide and released into solution by the reductive dissolution of the oxide. The relationship between ambient and lake spike HgT (r(2)=0.920, n=27, p<0.001) and MeHg (r(2)=0.967, n=23, p<0.001) indicated that similar biogeochemical processes control the temporal and spatial distribution in the water column. The larger fraction of MeHg in the lake spike compared to the ambient pool in the hypolimnion suggests that lake spike may be more available for methylation. A linear relationship of DOC to both filterable ambient HgT (r(2)=0.406, n=27, p<0.001) and lake spike HgT (r(2)=0.314, n=15, p=0.002) suggest a role of organic matter in Hg transport and cycling. However, a weak relationship between the ambient and lake spike pools of MeHg to DOC indicated that other processes have a major role in controlling the abundance and distribution of MeHg. Our results suggest that Fe and Mn play important roles in the transport and cycling of ambient and spike HgT and MeHg in the hypolimnion, in part through processes linked to the formation and dissolution of organic matter-containing Fe and Mn hydrous oxides particles.