On the potential of combining neutron activation analysis and particle induced X-ray emission (PIXE) for micro- and microdistribution analysis of hard metals in human tissues

Tungsten carbide and cobalt are the main components of hard metal alloy while other metals such as chromium, niobium, tantalum, titanium and vanadium are sometimes added in smaller amounts. Exposure to hard metal dusts can induce a lung fibrosis with cobalt playing a major role. In order to provide information on the role that each metal may have in causing this disease, determination of the total content and the distribution of inhaled metals in lung tissue of hard metal workers is of paramount importance. However, samples such as transbronchial biopsy and bronchoalveolar lavage (BAL), often used in the medical diagnosis of pneumoconiosis, only allow for a small amount of material. This calls for sensitive and accurate analytical procedures for microdetermination and distribution of metals in pulmonary tissue and cellular material, such as macrophages. This work proposes a combination of sophisticated analytical techniques such as neutron activation analysis (NAA), currently applied to the determination of the total concentration of more than 30 elements in biological specimens, and PIXE analysis, particularly microPIXE, which has a great potential for microdistribution analysis in small biological samples. Principles and perspectives for the combined use of these techniques for the analysis of human tissue are outlined and discussed. NAA: determination of hard metals in lung tissue are carried out by neutron irradiation (2 × 10¹⁴ neutrons cm⁻² s⁻¹) in the HFR reactor of Petten. After neutron activation, radiochemical separations of ⁶⁰Co, ¹⁸⁷W, ¹⁸²Ta, ⁵¹Cr followed by computer-based high resolution gamma ray spectrometry allow the measurement of these elements in pulmonary tissues with sensitivities ranging from 10⁻⁴ μg (Cr) to 10⁻⁶ μg (W). PIXE: this technique is multielemental and of relatively high sensitivity (μg/g) even in small total sample masses of from 10 to 100 μg, thus allowing the analysis of parts of needle biopsies. Whereas PIXE has been successfully applied to many medical problems, its usefulness is limited in the total samples analysis for cobalt-related hard metal disease, due to the low levels of cobalt in tissue combined with severe element interferences from the generally more abundant metal, iron. Nevertheless, microPIXE, a special variety of the method scanning over the sample with a focussed ion beam of about 2 × 2 μm², could complement the NAA findings in total samples in the sense of achieving a microdistribution analysis of hard metals (including cobalt) in suitable thin tissue sections.The availability of specialized facilities at the JRC such as the powerful HFR reactor (Petten), the NAA laboratories (Ispra) and the microPIXE facility (Geel) could represent a European ‘reference pole’ for the study of metals in tissues of hard metal diseased subjects.     

Metal determinations in biological specimens of diseased and non-diseased hard metal workers

Biological monitoring of Co, Ta and W, using mainly neutron activation analysis, was carried out on the urine, blood, pubic hair and toe nails of 251 subjects occupationally exposed to hard metal dusts (23 individuals were diagnosed as ‘diseased subjects’, affected by asthma and/or lung fibrosis). Airborne dust at hard metal workplaces were also analyzed for Co and W content. Cobalt and tungsten exposure at workplaces varied widely and frequently exceeded the TLV (0.05 mg Co/m³). Cobalt in urine (CoU), which is better than Co in blood (CoB), could represent a valuable indicator in discriminating between exposed groups, but is of little value as an indicator of exposure for single individuals. The high concentrations of cobalt in pubic hair (CoH) and toe nails (CoN) could also be valuable indicators of exposure although they are not useful, however, in establishing quantitatively the levels of cobalt accumulation. Tungsten and tantalum in pubic hair (WH and TaH) and toe nails (WN and TaN) also seem to be useful indicators in proving hard metal exposure qualitatively. The determination of these two elements, rather than cobalt, in the bronchoalveolar lavage (BAL) is very useful in complementing the diagnosis of hard metal disease proving hard metal exposure. The analysis of the BAL subfractions showed that W and Ta were firmly incorporated into the macrophage fraction while Co was distributed between cellular fraction and supernatant, which suggests a different mobility of hard metals in pulmonary tissue. The metal concentrations determined when submitted to statistical analysis indicated a positive correlation with P < 0.001 for the pairs (CoB---CoU), (Co---W) in urine, and (Co---W) in toe nails. Multielement analysis of biological specimens from diseased subjects suggests that hard metal disease does not relate to Co, W and Ta levels in the specimens considered. The disease does not depend on sex, age, working age and length of hard metal exposure. These findings support the theory on the possible haptenic properties of Co which may induce hypersensitivity and immuno-related toxic effects.     

Automated chemical analysis for measuring microgram levels of organic carbon in potable waters

An automated method for the direct determination of microgram levels of organic carbon in potable waters is described. The technique is that of continuous flow analysis and utilizes an automatic sampler, a multiple channel proportioning pump, and an appropriate analytical system (manifold). Samples are acidified, oxygen segmented and passed through a heated inorganic carbon stripper. The stripped liquid is resampled, mixed with silver peroxydisulphate solution and digested at 70°C. The liberated CO₂ is measured by means of infrared photometry. Complete inorganic carbon removal was not possible. From a 30 mg dm⁻³ inorganic carbon solution 0.1% residual remained after stripping. Using a sample volume of 6.3 cm³ min⁻¹, full-scale recorder deflection could be obtained for a 1 mg dm⁻³ organic carbon standard solution with a relative standard deviation of 0.9%. The lower detection limit of practical significance is 50 μg dm⁻³ organic carbon. The analysis rate is 20 samples per hour. Certain synthetic organic materials resisted complete oxidation and included the amino acids glycine, 1-alanine, leucine, iso-leucine and valine.     

An automated procedure for the determination of total Kjeldahl nitrogen

A procedure for the determination of total Kjeldahl nitrogen in surface fresh waters and organic wastes is described. Organic nitrogen compounds are converted to ammonium sulphate by a catalytic (red mercuric oxide) acid-sulphate digestion. The digest time is 3 h and allows for a maximum of 36 samples, 2 blanks and 2 standards to be processed simultaneously. There is no pH adjustment required following the digestion. Calibration curves covering the ranges (i) 0.5–100 μg NH₃---Nl⁻¹ and (ii) 10–1000 μg NH₃---Nl⁻¹ were linear within ±2%. The detection limit of the method is 0.5 μg TKNl⁻¹. The concentration range of TKN for which the method is suitable is 0.5 μg Nl⁻¹–40 mg Nl⁻¹. The method displayed a high tolerance to interferences from copper, iron, mercury and hardness. Digest procedure gave a high recovery and reproductibility over a wide range of nitrogen compounds tested.     

Automated determination of carbon in natural waters

An automated method for determining inorganic carbon and organic carbon in water is described. The sample is acidified and the CO₂ from inorganic carbonate is removed in a packed column and measured with an i.r. analyzer. The stripped liquid is pumped to a furnace containing cobalt oxide catalyst at 950°C where the organic carbon is oxidized; the resulting CO₂ is measured with an i.r. analyzer. Operating as a “two-channel” system, inorganic carbon and organic carbon are measured simultaneously at 20 samples per hour. If used in a “single-channel” mode, inorganic and organic carbon are measured separately, inorganic carbon at 60 samples per hour, organic carbon at 20 samples per hour. The coefficients of variation at 1 and 5 mg l⁻¹ organic carbon are 5.1 and 2.8% respectively. The detection limit is 200 μg l⁻¹C.     

Simultaneous determination of dissolved organic carbon and phosphorus in waters using flame ionization and photometric detectors

An apparatus with flame ionization and photometric detectors was assembled for the simultaneous determination of dissolved organic carbon (DOC) and phosphorus (DP) in waters. The optimum operating conditions were described. The long-term precision (relative standard deviation) is 5.8% for DOC and 5.2% for DP. The detection limits are 0.09 μg ml⁻¹ for DOC and 0.03 μg ml⁻¹ for DP. The responses for various DOC and DP compounds agreed almost with those obtained by combustion-infrared and persulfate digestion-colorimetric methods, respectively. DOC and DP in several water samples were determined by this method and other methods, and the results obtained by those methods were discussed.     

Complexation analysis of fresh waters by equilibrium diafiltration

Equilibrium ultrafiltration has been employed to determine the extent of Cu, Ni, Co, Fe, Mn and Zu chelation in oxic waters from mineralized terrains. Concentrations of Cu, Ni and Co were determined in different organic fractions separated by various Amicon ultrafilters. Titrations of fresh water samples with metal ions were made, and “free” metal concentration measured by equilibrium diafiltration. Experiments were made at concentrations and pH at which metals and ligands occur in natural waters. Conditional stability functions ranged from 10^6.72 at pH 6.5 to 10^7.07 at pH 7.6 for Ni and 10^6.85 at pH 6.8 to 10^6.97 at pH 7.6 for Co. At low metal concentrations (8 × 10⁻⁷ M) only one complexing class of major importance for natural water environments was observed. The order of metal complexing ability was found to be Cu > Ni > Co > Zn > Mn with Cu showing a preference towards the higher MW organic fractions.     

Investigation of the Folin-Ciocalteau phenol reagent for the determination of polyphenolic substances in natural waters

The methodology associated with the Folin-Ciocalteau phenol reagent was investigated and the performance characteristics of a method using sodium carbonate as the supporting medium were determined. Calibration curves using phenol, tannic acid, or l-tyrosine were linear up to at least 1000 μg l⁻¹. The limit of detection was 6 μg phenol l⁻¹ and the relative standard deviation at 100 μg phenol l⁻¹ was 5.2% and at 1000 μg phenol l⁻¹ was 4.1%. The absorbances obtained with equal amounts of a range of potential standards showed variations when compared with that of phenol: phenol (100%), l-tyrosine (62%), oak gall tannin (58%), tannic acid (48%), chestnut tannin (26%), oak tannin (24%), fulvic acid (5%). The method was applicable to a wide range of monohydric and polyhydric phenolic substances and interferences from inorganic and non-phenolic organic compounds were examined. Interference would be expected above 30 μg S²⁻ l⁻¹, 300 μg Mn(II) l⁻¹, or 400 μg SO₃²⁻ l⁻¹. Concentrations of iron >2 mg l⁻¹ as Fe(II) or Fe(III) formed the insoluble iron(III) hydroxide which increased the absorbance, but centrifugation could be used to remove this source of interference. Other potential sources of intereference (e.g. reducing agents and certain metabolic products) would be expected to have a negligible effect in unpolluted waters. Methods using diazotised sulphanilic acid or 4-aminoantipyrine (4-AAP) were found to be inferior when applied to natural water samples.     

The effects of organotin on the activated sludge process

Organotin compounds which find increasing use in marine antifouling paints may be present in the discharge from dry dock operations. This investigation was aimed at determining the effect of such wastewater when discharged to a municipal activated sludge treatment plant. Experiments were conducted using a Warburg respirometer and continuous flow bench-scale activated sludge systems. The results showed that unacclimated biological cultures can be inhibited by tributyl tin oxide (TBTO^™) concentrations as low as 25 μgl⁻¹. However, TBTO doses of over 8000 μgl⁻¹ can be tolerated by a well acclimated culture. Continuous loading of up to 1000 μgl⁻¹ TBTO had no effect on organic removal in activated sludge systems. However, an adverse effect on sludge settleability was noticed at 100 μgl⁻¹ TBTO. Shock loadings of 500 and 1000 μgl⁻¹ TBTO had no effect on soluble organic removal but resulted in impaired settling and higher effluent suspended solids. The LC₅₀ of TBTO to the fathead minnow was estimated at 45–200 μgl⁻¹. The toxicity was reduced considerably by activated sludge treatment.     

Chlorophenols in surface waters of the Netherlands (1976–1977)

In this paper an analytical method is described for the capillary gas chromatographic determination, after derivatization, of 19 individual chlorophenols in surface water. The minimum detectable amounts are for monochlorophenols 2 μg l⁻¹, for dichlorophenols 0.05 μg l⁻¹, for trichlorophenols 0.02 μg l⁻¹ and for tetra- and pentachlorophenols 0.01 μg l⁻¹. The results of a monitoring program in the river Rhine and other Dutch surface waters with respect to these compounds are presented. The results cover the period January 1976–December 1977. 2,6-Dichlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachlorophenol had the highest frequencies of occurrence in the river Rhine and its tributaries. Pentachlorophenol was found in the highest concentrations (up to 11 μg l⁻¹).     

Distribution of species of Cu, Pb, Zn and Cd in a water profile of the Yarra river estuary

The behaviour of Cu, Pb, Zn and Cd in a highly stratified estuary was examined. The distribution of ionic and ‘organically bound” forms of the metals was determined by differential pulse anodic stripping voltammetry (dpasv) before and after u.v. irradiation. The two forms of the metals were compared with the water characteristics of salinity, temperature, turbidity, flow, and inorganic and organic carbon.Irradiation increased the concentration of all four elements detectable by dpasv. The greatest increase was for Cu in the 1 m depth river water which yielded 7.5 μg l⁻¹ before irradiation and 29 μg l⁻¹ after irradiation. Cu and Cd showed minimum concentrations in the seawater layer at 4 m depth, corresponding to the fresh seawater flowing upstream below the halocline. The concentrations of Cu and Cd were higher in the river water than in the underlying seawater. Zn concentration in the river water was lower than in the seawater. Relationships between the trace metal concentrations and the characteristics of the water column are not clear, but the direction of water movement is a major influence.     

Acute and chronic toxicity of lead to rainbow trout salmo gairdneri, in hard and soft water

Lead was found to be highly toxic to rainbow trout in both hard water (hardness 353 mg l⁻¹ as CaCO₃) and soft water (hardness 28 mg l⁻¹. Analytical results differ greatly with methods of analysis when measuring concentrations of lead in the two types of water. This is exemplified in LC50's and maximum acceptable toxicant concentrations (MATC's) obtained when reported as dissolved lead vs total lead added in hard water. Two static bioassays in hard water gave 96-h LC50's of 1.32 and 1.47 mg l⁻¹ dissolved lead vs total lead LC50's of 542 and 471 mg l⁻¹, respectively. In a flow-through bioassay in soft water a 96-h LC50 of 1.17 mg l⁻¹, expressed as either dissolved or total lead, was obtained. From chronic bioassays, MATC's of lead for rainbow trout in hard water were between 18.2 and 31.7 μg l⁻¹ dissolved lead vs 120–360 μg l⁻¹ total lead. In soft water, where exposure to lead was initiated at the eyed egg stage of development, the MATC was between 4.1 and 7.6 μg l⁻¹. With exposure to lead beginning after hatching and swim-up of fry, the MATC was between 7.2 and 14.6 μg l⁻¹. Therefore, fish were more sensitive to the effects of lead when exposed as eggs.     

Toxicity of sodium selenite to rainbow trout fry

In a study designed to examine the long-term effects of inorganic selenium (IV) on early life stages of rainbow trout (Salmo gairdneri), survival was significantly reduced at selenium concentrations of 47 and 100 μg l⁻¹ after 90 days of exposure. Length and weight were significantly reduced after 90 days of exposure to 100 μg l⁻¹. Whole-body residues of selenium increased with increasing exposure concentrations but appeared to decline between 30 and 90 days of exposure. Analyses of trout backbone indicated little change in bone development with exposure to selenium (IV) with one exception; calcium concentrations were significantly decreased in fish exposed to 12 μg l⁻¹ of selenium. Results of our study indicates that a recommended safe level of 10 μg l⁻¹ for inorganic selenium would not significantly affect growth and survival of rainbow trout; however, concentrations of selenium near this level can reduce the levels of calcium in the backbones of trout.     

Chlorophenols in river sediment in The Netherlands

In this paper an analytical method is described for the capillary gas chromatographic determination, after derivitization, of 19 individual chlorophenols in river sediment. The minimum detectable amounts are for monochlorophenols 10 μg kg⁻¹, dichlorophenols 0.5 μg kg⁻¹, trichlorophenols 0.2 μg kg⁻¹ and for tetra- and pentachlorophenols 0.1 μg kg⁻¹. The results of a monitoring program in the Rhine River and its tributaries and other Dutch surface waters with respect to these compounds are presented. 2,5-Dichlorophenol, 2,3,5- and 2,4,5-trichlorophenol, 2,3,4,5- and 2,3,4,6-tetrachlorophenol and pentachlorophenol had a frequency of occurrence of 100% in sediment samples from Lake Ketelmeer, which is a deposition area for Rhine River sediment. The highest concentrations of chlorophenols were found in the Nieuwe Maas River near Rotterdam, a heavily industrialized area.     

Application de la spectrometrie d'absorption atomique zeeman aux dosages de huit elements traces (Ag, Cd, Cr, Cu, Mn, Ni, Pb et Se) dans des matrices biologiques solides

The use of biological indicators in studies of aquatic pollution (in fresh, estuarine or sea waters), as well as research about the metal transfers in food chains, need a great accuracy of the trace element determination. Therefore, as shown by the results of international intercalibration exercises, the mastery of analytical techniques is far from being perfect in all the laboratories.One of the main sources of error in atomic absorption results from non-specific absorptions due to the presence of important organic and mineral matrixes in biological materials and especially in aquatic and marine organisms. In this case, the correction of unspecific absorption by using deuterium lamp was insufficient and the determination of trace elements had to be preceded by a pre-instrumental stage which allowed the elimination of the organic matter by mineralization and of a large part of the mineral matrix by extraction. The previous separation was long and induced contamination risks. The use of the Zeeman effect background correction allows the transfer of most processes from the pre-instrumental to the instrumental stage. Moreover, the Zeeman effect has three advantages: (1) the background correction is effective up to 2 units of absorbance; (2) the correction is effective from 190 to 900 nm; (3) the method of the double beam is optimalized.The aim of this study was to apply the Zeeman effect to the determination of eight trace elements (Ag, Cd, Cr, Cu, Mn, Ni, Pb, Se) in three different biological solid samples, two originated from the marine environment (lobster hepatopancreas TORT-1, standard reference material from the National Research Council Canada; oyster tissues SRM 1566 from the US National Bureau of Standards) and one from the vegetable kingdom (tomato leaves, SRM 1573 from the US NBS).The experimental procedure is reduced to a minimum since it consists in the digestion of an aliquot of 100 mg of the powdered sample with 1 ml of concentrated nitric acid at 95°C for 1 h. Then the volume is adjusted to 4 ml with deionized water. The metal analysis is carried out using a graphite furnace coated with tantalum carbide.This analysis is achieved according to the method of standard addition. The three added concentrations used for each element are listed in Table 1. The analytical conditions and graphite atomizer program are indicated in Table 2. The temperature program has to be modified according to the type of equipment.The internal quality control of the suggested method related to four criteria: sensitivity, repeatability, accuracy, practicability. The results are shown in Table 3. The threshold of sensitivity (3 times the SD of a series of eight results obtained for a blank of digestion) are low: < 1 μg kg⁻¹ for Ag, Cd and Mn; 1 μg kg⁻¹ for Cr and Pb; 5 μg kg⁻¹ for Cu and Ni and 15 μg kg⁻¹ for Se. The variation coefficients, calculated for both two series of six determinations each, are generally included between 5 and 10%. The trace element concentrations determined by using this method are in perfect agreement with the certified values of the US NBS and NRC Canada (Table 3.)The quality of the results establishes the possibility of using a very easy and fast method to determine the level of eight trace elements in materials with high mineral and organic matter content.     

Chlorinated organics from chlorine used in water treatment

The contribution from impurities in chlorine to levels of chlorinated organics found in potable water after chlorination was investigated. Techniques for sampling of chlorine and gas chromatography (GC) determination of chlorinated organics in chlorine are described. The detection limits were better than 1 ppm for each of chloromethane, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, tetrachloroethylene, hexachloroethane, hexachloropropane and hexachlorobenzene in chlorine. With the exception of chloroform which occasionally accounted for nearly 1 μg l⁻¹ in water, the levels of the nine compounds in chlorine accounted for less than 0.1 μg l⁻¹ of each compound in chlorinated water from 10 Canadian treatment plants. The occurrence of these nine and 28 additional chlorinated organics previously detected in water supplies was determined by aid of liquid-liquid extraction of water samples. Seven compounds, including chloroform, carbon tetrachloride, trichloroethylene and tetrachloroethylene were detected, usually at levels ranging from 0.1 to 1 μg l⁻¹ in chlorinated water from the treatment plant.     

Note on a rapid and sensitive method for the determination of anionic detergents in natural waters at the ppb level

A rapid and sensitive method for the determination of anionic detergents in natural waters is developed using atomic absorption spectrophotometry and his (ethylenediamine) copper(II) ion. The method is suitable for a concentration range of 0–50 μg1⁻¹ (ppb), but its applicability can be extended up to 15 μg ml⁻¹. The limit of detection is 0.3 μg l⁻¹.     

Accumulation de quelques metaux lourds (Cd, Cu, Pb et Zn) chez l'eperlan (Osmerus mordax) preleve sur la rive Nord de l'Estuaire du Saint-Laurent

Heavy metals in trace amounts are normal constituents of marine organisms. At sufficiently high concentrations, heavy metals are toxic to living organisms and so it is important to know by how much their concentration may be increased before effects on marine or estuarine populations can be detected or commercial species become unsuitable as food. A method of removing metals is by storage in a particular tissue. Several different sites for storing metals were investigated and concentrations of Cd, Cu, Pb and Zn were examined in muscle, liver and gonads of the smelt (Osmerus mordax) from the North shore of the St Lawrence estuary. Copper and zinc are constituents of several enzymes and are absolutely essential for normal growth and development, while cadmium and lead are not known to have necessary physiological function. A modified wet digestion procedure was used to prepare biological samples for the determination of trace elements by flameless atomic absorption spectrophotometry procedure, using calibration standards made up in a matrix of similar acidity (Table 1). NBS reference material bovine liver was analyzed along with the samples and the results were within the specified tolerance (Table 2). Analyses were reported on a dry weight basis (Table 3) and the correlations with total body weight were determined by regression analysis. Copper (range 0.3–3.3 μg g⁻¹) and zinc (range 19–38 μg g⁻¹) in muscle fillets were found to be negatively correlated with total body weight (Fig. 1). Apparent decreasing concentrations in these two metal levels in muscle sample with increasing body weight were possibly due to factor such as dilution with growth. Growth may dilute metal concentrations in an organism if tissue is added faster than metal. Livers and gonads contained greater levels of the four metals than somatic muscle. Liver metal concentrations of Zn (range 29–108 μg g⁻¹) and Cd (range 0.06–0.37 μg g⁻¹) increased with total body weight. All equations fit data at P < 0.01 (Fig. 2). Positive correlations between size and metal concentrations suggest that net uptake may occur. Inessential, slowly exchanging metals such as Cd appear to reflect an uptake which tend to become a cumulative process (age dependence of concentrations). The occurrence of insignificant correlation between liver concentrations of Cu (mean value: 4 μg g⁻¹) and environmental concentrations of this metal was consistent with equilibration. Since fish are known to possess the metal binding protein metallothionein, a sequestering agent, detoxification of these metals in fish liver may be by sequestration rather than elimination. Increasing metal concentrations in liver may represent storage of sequestered products in that organ. In the gonads, no significant relationship exists between total body weight and trace metal contents. Results of t-test indicated that females had significantly greater Cu and Zn concentrations, but no significant difference existed between males and females for Cd concentrations (Figs 3 and 4). Thus, the relation between concentration and total body weight appears to be specific as to the species, tissues analyzed and environmental conditions. The comparison of metal concentrations in fish to assess variations in contamination levels requires understanding the relationship between metal concentration and body size within each population.     

Time-dependent variation of mercury in a stream sediment and the effect upon mercury content in Gammarus pulex (L.)

A 3-month investigation has been carried out in a stream environment, on the fluctuation of the level of mercury within the sediment and the Gammarus pulex population. A positive correlation is found between the organic content and the mercury content (μg g⁻¹ dry wt) of the samples. The mean mercury concentration in the organic fraction can be read from the regression line. Of the units: μg g⁻¹ dry wt, μg g⁻¹ ashfree dry wt and μg cm⁻³, the values expressed g⁻¹ ashfree dry wt are considered to be of greatest validity for comparing different localities, and for establishing the pollution level in a stream sediment. Within the investigation period a very high fluctuation is found in the mercury content of analyzed Gammarus pulex. The phenomenon may be explained through fluctuations in the methylating processes within the sediment. No positive correlation is found between mercury in Gammarus pulex and in sediement taken from identical sample locations.     

Trace organic behavior in soil columns during rapid infiltration of secondary wastewater

Secondary treated municipal wastewater from the City of Phoenix was applied to three laboratory-scale soil columns at various infiltration rates typical of high-rate land application systems, and a fourth column was inundated with tapwater to serve as a control. Samples of the column influent and effluent streams, collected with continuous flow-through systems to prevent organic volatilization losses, were analyzed for organic compounds using gas chromatography/mass spectrometry. The secondary wastewater contained chloroform, 1,1,1-trichloroethane, and tetrachloroethylene in the range of 1–10 μg l⁻¹. These compounds also were present in the soil column effluents apparently with complete breakthrough of chloroform. Also present in the column influents and effluents were up to 1 μg l⁻¹ of hydrocarbons, alcohols, ketones, chlorinated and unchlorinated aromatics, phthalates, chlorinated anisoles, a few pesticides, and several unknown compounds. Several compounds present in the secondary wastewater were not found in the column effluents. Conversely, a few compounds found in the column effluents were not detected in the wastewater. For many compounds, column effluent concentrations were lower than column influent values. Infiltration rate over the range studied did not influence the degree of organic removals observed. The tapwater column effluent contained the same compounds and concentrations as the other columns, which suggests prior storage and leaching of the organic compounds from the soil. This study was performed to give a general indication of the behavior of trace organics in soil column systems with an attempt to indicate the presence of various removal processes. Evidence is given for biodegradation, sorption, and volatilization.