Concentrations and bioaccessibility of polycyclic aromatic hydrocarbons in wastewater-irrigated soil using in vitro gastrointestinal test

BACKGROUND, AIM, AND SCOPE: Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental contaminants and contribute to the pollution of soil environment. Soil ingestion is of increasing concern for assessing health risk from PAH-contaminated soils because soil ingestion is one of the potentially important pathways of exposure to environmental pollutants, particularly relevant for children playing at contaminated sites due to their hand-to-mouth activities. In vitro gastro-intestinal tests imitate the human digestive tract, based on the physiology of humans, generally more simple, less time-consuming, and especially more reproducible than animal tests. This study was conducted to investigate the level of PAH contamination and oral bioaccessibility in surface soils, using physiologically based in vitro gastro-intestinal tests regarding both gastric and small intestinal conditions. MATERIALS AND METHODS: Wastewater-irrigated soils were sampled from the metropolitan areas of Beijing and Tianjin, China, which were highly contaminated with PAHs. Reference soil samples were also collected for comparisons. At each site, four soils were sampled in the upper horizon at the depth of 0-20 cm randomly and were bulked together to form one composite sample. PAH concentrations and origin were investigated and a physiologically based in vitro test was conducted using all analytical grade reagents. Linear regression model was used to assess the relationship between total PAH concentrations in soils and soil organic carbon (SOC). RESULTS: A wide range of total PAH concentrations ranging from 1,304 to 3,369 mug kg(-1) in soils collected from different wastewater-irrigated sites in Tianjin, while ranging from 2,687 to 4,916 mug kg(-1) in soils collected from different wastewater-irrigated sites in Beijing, was detected. In general, total PAH concentrations in soils from Beijing sites were significantly higher than those from Tianjin sites, indicating a dominant contribution from both pyrogenic and petrogenic sources. Results indicated that the oral bioaccessibility of PAHs in small intestinal was significantly higher (from P < 0.05 to P < 0.001) than gastric condition. Similarly, the oral bioaccessibility of PAHs in contaminated sites was significantly higher (from P < or = 0.05 to P < 0.001) than in reference sites. Individual PAH ratios (three to six rings), a more accurate and reliable estimation about the emission sources, were used to distinguish the natural and anthropogenic PAH inputs in the soils. Results indicated that PAHs were both pyrogenic and petrogenic in nature. DISCUSSION: The identification of PAH sources and importance of in vitro test for PAH bioaccessibility were emphasized in this study. The oral bioaccessibility of individual PAHs in soils generally decreased with increasing ring numbers of PAHs in both the gastric and small intestinal conditions. However, the ratio of bioaccessibility of individual PAHs in gastric conditions to that in the small intestinal condition generally increased with increasing ring numbers, indicating the relatively pronounced effect of bile extract on improving the bioaccessibility of PAHs with relatively high ring numbers characterized by their high K ( ow ) values. Similarly, total PAH concentrations in soils were strongly correlated with SOC, indicating that SOC was the key factor determining the retention of PAHs in soils. CONCLUSIONS: Soils were contaminated with PAHs due to long-term wastewater irrigation. PAHs with two to six rings showed high concentrations with a significant increase over reference soils. Based on the molecular indices, it was suggested that PAHs in soils had both pyrogenic and petrogenic sources. It was also concluded that the oral bioaccessibility of total PAHs in the small intestinal condition was significantly higher than that in the gastric condition. Furthermore, the bioaccessibility of individual PAHs in soils generally decreased with the increasing ring numbers in both the gastric and small intestinal conditions. RECOMMENDATIONS AND PERSPECTIVES: It is suggested that more care should be given while establishing reliable soil criteria for PAHs, especially concerning the health of children who may ingest a considerable amount of PAH-contaminated soil via outdoor hand-to-mouth activities.     

Effect of cropping and tillage on the dissipation of PAH contamination in soil

This study examined the effect of regular tillage and cropping on the dissipation rate of PAHs in contaminated soil. Lysimeters were placed under natural climatic conditions for 2 years and designed to measure the concentration of PAHs in soil and leachates and their toxicity. The soil initially contained 2077 microg PAHs g(-1). The largest decrease in PAHs concentration occurred during the first 6 months. No further significant decrease was observed after this time. The surface soil layer always contained significantly less PAHs than the deeper layer, regardless of the treatments. Less than 8.4 x 10(-8)% of the PAH initially present in the soil (e.g. less or equal to 33 microg PAHs per lysimeter) were leached from the soils during the experiment and the leachates presented no toxicity (as measured by the Microtox test). The toxicity of the soils decreased with time and was significantly lower on the cropped soil compared to the other treatments, despite the residual concentration of PAHs being the highest in this soil. This study demonstrated that the dissipation rates of PAHs were slow after using natural attenuation even when tillage and cropping were performed at the soil surface.     

The effect of soil organic matter on fate of polycyclic aromatic hydrocarbons in soil: A microcosm study

A microcosm study was conducted to address the influences of air-soil partition and sequestration on the fate of polycyclic aromatic hydrocarbons (PAHs) in soil. Sterilized and unsterilized soils with soil organic carbon (SOC) content ranging from 0.23 to 7.06% were incubated in a chamber with six PAHs supplied through air. After 100 d of incubation when the system approached pseudo-steady state, the PAHs concentrations in the unsterilized soils still correlated with SOC significantly, while the association did not exist for those sterilized. The lower degradation rate in the soil with higher SOC was likely the major reason for the association between SOC and PAHs concentrations, while the decreased surface porosity likely suppressed such correlation for the sterilized samples. The results indicated that the sequestration was likely the major mechanism for the accumulation of PAHs in soils, while both of the soil porosity and PAHs properties had observed influences.     

Persistence of polycyclic aromatic hydrocarbons (PAHs) in sewage sludge-amended soil

The application of sewage sludge as a fertilizer is a common method used to improve soil properties. However, sewage sludge may contain various organic pollutants including polycyclic aromatic hydrocarbons. In the present study, the persistence of PAHs in soils fertilized with different sewage sludge doses was compared in relation to the sewage sludge dose applied (30, 75, 150, 300 and 600 Mgha(-1)) and the content of the polycyclic aromatic hydrocarbons in them. The experiment was carried out in two blocks of experimental plots divided according to the type of plants grown: field plants and perennial-willow. Sewage sludge addition to soils resulted in an increase in the content of polycyclic aromatic hydrocarbons in these soils. This increase was proportional to the quantity of sewage sludge applied. The results obtained showed that during a 42/54-month period, more than half of the individual PAHs introduced into the soil with sewage sludge were degraded. The scope of dissipation depended on the sewage sludge dose and the use to which the area was put. In the experiment with the willow only in the case of the highest sludge dose was a decrease in the PAH content above 50% noted; whereas in the case of the experiment with the field plants, it was higher by 50% for all sewage sludge doses. In experiment with field plants the highest scope of individual PAH disappearance was observed in the soil with the sewage sludge dose amounting to 300 Mgha(-1). In experiment with willow a relatively high dissipation of individual PAHs (>50%) was found in the treatment with the highest sludge dose (600 Mgha(-1)). A wider PAH dissipation range in the experiment with field plants was conditioned by the more favourable conditions created as a result of the breeding treatments applied. Agrotechnical treatments clearly increased the disappearance of the PAHs in those soils fertilized with the lowest sewage sludge doses (30 and 75 Mgha(-1)). The results obtained showed that the preferred method of treating a light soil fertilised with sewage sludges should be a one-year system, with a sludge application of 75 Mgha(-1).     

The role of soil and active ingredient properties in degradation of pesticides: A preliminary assessment

Pesticide disappearance from soils was observed in laboratory studies in which leaching and runoff were impeded, and volatilisation and degradation evaluated. Advection by volatilisation was negligible for the less volatile chemicals, and significant for the more volatile (Trifluralin and Heptachlor). Basic statistics applied to degradation DT50 data of 14 active ingredients in four different soils showed that the properties of pesticides play a major role in determining their degradability.     

Assessment of the bioaccessibility of polycyclic aromatic hydrocarbons in soils from Beijing using an in vitro test

As an important human exposure pathway of contaminants, soil ingestion is of increasing concern for assessing health risk from polycyclic aromatic hydrocarbons (PAHs) in soils. A wide range of total PAH concentrations ranging from 0.112 microg g(-1) to 27.8 microg g(-1) in soils collected from different public sites, including gas stations, roadsides, bus stops, a kindergarten, primary and middle schools, a university and residential area, was detected. In general, total PAHs concentrations in soils from traffic areas were significantly higher than that from the other sites, indicating a dominant contribution from motor vehicles. Physiologically based in vitro tests were used to evaluate the oral bioaccessibility of PAHs in surface soil under different land uses in Beijing regarding both gastric and small intestinal conditions. It was found that the oral bioaccessibility of total PAHs in small intestinal condition, ranging from 9.2% to 60.5% of total PAHs in soil, was significantly higher than gastric condition, ranging from 3.9% to 54.9%. The bioaccessibility of individual PAHs in soils generally decreased with the increasing ring number of PAHs in both gastric and small intestinal conditions. However, the ratio of bioaccessibility of individual PAHs in gastric condition to that in small intestinal condition, generally increased with increasing ring number, indicating the relatively pronounced effect of bile extract on improving bioaccessibility of PAHs with relatively high ring numbers characterized by their high K(ow) values. The observation that bile extract at a level higher than critical micelle concentration could reduce the surface tension of digestive juice substantially, which may cause PAHs to be available for intestinal absorption, calls for more careful establishment of reliable soil criteria for PAHs, especially concerning the health of children who may ingest a considerable amount of PAH-contaminated soil via outdoor hand-mouth activities.     

Monitoring of the total content of polycyclic aromatic hydrocarbons (PAHs) in arable soils in Poland

The paper provides comprehensive information on the level of contamination of arable soils in Poland with polycyclic aromatic hydrocarbons (PAHs). Extensive monitoring studies were carried out to determine the content of the 16 priority PAHs in 216 soil samples collected in 2005 throughout arable lands (0-20 cm layer) in Poland. Locations of sampling points reflected the differences in regional industrialisation and urbanisation as well as in the characteristics of soils. The content of Sigma16PAHs ranged from 80 to 7264 microg kg(-1) with a median of 395 microg kg(-1) and with a dominance of 4-6 rings hydrocarbons (74% of total PAHs). Soil properties affected the PAHs content to a limited extend. The organic matter content was the only parameter correlated significantly (although weakly) with the concentrations of Sigma16PAHs; the strength of this relationship was more pronounced in soils with elevated OM content. The various molecular markers pointed to a prevailing pyrogenic origin of the PAHs in Polish arable soils, with minor contribution from liquid fuels combustion and traffic emissions. Two different Polish systems for classification of agricultural soils (providing for the content of Sigma9PAHs and Sigma13PAHs) indicate that the percentage of contaminated arable soils in Poland does not exceed 10%. Multivariate methods enabled an evaluation of spatial trends in Sigma16PAHs concentrations, an identification of regions with very low PAHs content (East part of the country), and a recognition of small industrial/urbanised areas of higher risk.     

Comparative study of extraction methods for the determination of PAHs from contaminated soils and sediments

The following four methods were compared on the extraction efficiency of 16 EPA (US Environmental Protection Agency) polycyclic aromatic hydrocarbons (PAHs): German method of the Verband Deutscher Landwirtschaftlicher Untersuchungs und Forschungsanstalten (VDLUFA), two methods of the International Organization for Standardization using shaking (ISO A) and Soxhlet extraction (ISO B) and an ultrasonic method. Recovery rates of 16 PAHs were determined in two soils. Extraction efficiency was evaluated in five soils and three sediments. Effect of drying soils and sediments on extraction efficiency was tested using the VDLUFA and the ultrasonic methods. Our study shows that the number of aromatic rings, rather than extraction procedures, significantly influenced recovery rates of individual PAHs. No significant differences in extraction efficiency of the four methods were observed for less polluted samples. For highly polluted soils, extraction efficiency decreased in the following order: VDLUFA method > ISO A > ultrasonic method > ISO B. Influence of soil moisture on extraction efficiency depended to some extent on both solvent used and content of PAHs in samples. A mixture of dichloromethane/acetone (5:1) is recommended for PAH extraction from moist samples when the ultrasonic method is used.     

Polycyclic aromatic hydrocarbons in ash: determination of total and leachable concentrations

Before wood ash can be used as a soil fertilizer, concentrations of environmentally hazardous compounds must be investigated. In this study, total and leachable concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in four ash samples and one green liquor sludge. The ash sample with the highest carbon content also contained high levels of PAHs; three of the ash samples had total concentrations exceeding the limit permitted by the Swedish Forest Agency for recycling to forest soils. The leachable concentrations were higher for the non-stabilized samples; this was probably due to colloid-facilitated transport of the contaminants in these samples. However, the leachable concentrations were overall relatively low in all the samples studied. The amounts of PAHs introduced to forest soils by additions of stabilized, recyclable ash products will be determined primarily by the rate of weathering of the ash particles and the total concentration of contaminants.     

Dissipation of polycyclic aromatic hydrocarbons (PAHs) in the rhizosphere: Synthesis through meta-analysis

Polycyclic aromatic hydrocarbons (PAHs) are widespread and persistent organic pollutants with high carcinogenic effect and toxicity; their behavior and fate in the soil-plant system have been widely investigated. In the present paper, meta-analysis was used to explore the interaction between plant growth and dissipation of PAHs in soil based on the large body of published literature. Plants have a promoting effect on PAH dissipation in soils. There was no difference in PAH dissipation between soils contaminated with single and mixed PAHs. However, plants had a more obvious effect on PAH dissipation in freshly-spiked soils than in long-term field-polluted soils. Additionally, a positive effect of the number of microbial populations capable of degrading PAHs was observed in the rhizosphere compared with the bulk soil. Our meta-analysis established the importance of the rhizosphere effect on PAH dissipation in variety of the soil-plant systems.     

Effect of metals on the adsorption and extractability of 14C-phenanthrene in soils

The fate of polycyclic aromatic hydrocarbons (PAHs) in contaminated soils may be affected by several environmental factors including the presence of co-contaminants. This study was conducted in order to assess the effect of metals on (i) the adsorption of 14C-phenanthrene in soils and (ii) its extractability and ability to form non-extractable residues. The first objective was accomplished using batch adsorption experiments with an uncontaminated agricultural soil spiked with the metals Cd, Cu, Pb, and Zn. Adsorption of phenanthrene was significantly higher after the addition of the metals (Kf = 21.48 vs. 8.55) and the desorption less readily reversible when compared to the unspiked soil. The extractability of phenanthrene was assessed with incubation (4 months, laboratory conditions) and microlysimeter experiments (6 months, natural climatic conditions) on three soils spiked with metals. All the soils were labelled with 14C-phenanthrene. The amount of extractable phenanthrene residues was significantly higher when the metals had been added to the soils. Nevertheless, the quantity of non-extractable residues was non-significantly different between the spiked and unspiked soils. The mechanism leading to increased adsorption and extractability of phenanthrene in the presence of metals is still unknown. In perspective, it would be interesting to assess the bioavailability of PAHs in the presence of metals in further experiments.     

Polycyclic aromatic hydrocarbons in the surface soils from outskirts of Beijing, China

Surface soils from the outskirts of Beijing were analyzed for 16 priority polycyclic aromatic hydrocarbons (PAHs) using gas chromatography and mass spectrometry (GC-MS). The distribution map of total PAHs content was obtained as a contour plot. The concentration range of 16 PAHs varied by over two orders of magnitude from 0.016 microg g-1 in rural to 3.884 microg g-1 in suburban soils with the relatively standard deviation of 70.5%, showing large differences in the extent of PAHs pollution at the various sampling sites. It was notable that the concentration of BaP was 0.005-0.270 microg g-1 with a mean of 0.055 microg g-1. In general, the distribution of PAHs centered on the high molecular weight PAHs known to be carcinogenic. The 4-6 ring PAHs represented about 66% in rural samples and 70% in suburban soils of the total PAHs found. There was relatively good relationship among most of the individual PAHs and the compounds of Pyr, BaA, Flu, BbF, BaP, Chr and Ph gave strong correlation (r>0.8) with the sum of PAHs. The selected marked compounds, a principal component analysis (PCA) and special PAHs compound ratios (Ph/An vs Flu/Pyr; summation operator COMB/ summation operator EPA-PAHs) suggest the pyrogenic origins, especially traffic exhausts, are the dominant sources of PAHs in Beijing outskirts soils.     

Behavior of PAHs during cold storage of historically contaminated soil samples

The stability of historically polycyclic aromatic hydrocarbon (PAH)-contaminated soils during cold storage was investigated. Samples from two former manufactured gas plants exhibited quantitative recoveries of PAHs over the whole period of sample holding at 4 °C in the dark (8–10 months), whereas significant losses of PAHs were observed for soils received from a former railroad sleeper preservation plant with low molecular weight compounds being notably more affected compared to heavier PAHs. Already after 2 weeks of holding time, 3-ring PAHs in one of theses samples were down to 29–73% of the initial concentration and significant losses were observed for up to 5-ring compounds. Dissipation of PAHs was found to be predominantly due to aerobic microbial metabolism since sodium azide poisoned samples showed quantitative recoveries for all PAHs over the entire storage time of 3 months. A similar stabilizing effect was observed for freezing at −20 °C as means of preservation. Except for acenaphthene, no significant loss for any of the PAHs was observed over 6 weeks of holding time. Eventually, selected chemical, physical, and biological parameters of two soils were investigated and identified as potential indicators for the stability of PAH-contaminated soil samples.     

Fate of 14C‐allylalcohol herbicide in soils and crop residues

Abstract

Residue disappearance and leaching of ¹⁴C‐allyl‐alcohol from different soils were studied in laboratory experiments. Additionally, the uptake of residues by lettuce and carrots was investigated in the greenhouse. In laboratory experiments, residue disappearance and leaching from soils was correlated negatively to the organic matter content. In greenhouse experiments with a sandy loam soil at an application rate normally used in practice, an average of 12.5 % of the applied radioactivity was recovered after an eight day interval between application and sowing. Furthermore, an average of 8 % (sum in soil and plants) of the applied radioactivity was recovered after lettuce or carrot growing. Uptake of residues was higher by carrots than by lettuce, and higher by lettuce roots than by lettuce tops. No bioaccumulation was observed. The residues in soils and plants were, to a high percentage, unextractable and, to a smaller extent, fully water‐soluble products. Unchanged allylalcohol could not be detected by the analytical methods used.     

Distribution and sources of polycyclic aromatic hydrocarbons from urban to rural soils: a case study in Dalian, China

To estimate the distribution and sources of soil polycyclic aromatic hydrocarbons (PAHs) in metropolitan and adjacent areas, soil samples were collected from urban, suburban and rural locations of Dalian, China, and concentrations of 14 PAHs were determined. The spatial PAH profiles were site-specific and determined by the sources close to the sampling sites. PAH concentrations decreased significantly along the urban-suburban-rural transect. The gradient implied that the fractionation effect influenced PAH distribution. Bivariate plots of selected diagnostic ratios showed general trends of co-variation and allowed to distinguish samples taken from different areas. An improved method, factor analysis (FA) with nonnegative constrains, was used to determine the primary sources and contributions of PAHs in soils. The FA model showed traffic average (74%) and coal related residential emission (26%) were two primary sources to Dalian soils. In addition, the FA model provided reasonable explanations for PAH contributions in soils from different sites. The results suggest that FA with nonnegative constraints is a promising tool for source apportionment of PAHs in soils.     

Application of magnetite-activated persulfate oxidation for the degradation of PAHs in contaminated soils

In this study, feasibility of magnetite-activated persulfate oxidation (AP) was evaluated for the degradation of polycyclic aromatic hydrocarbons (PAHs) in batch slurry system. Persulfate oxidation activated with soluble Fe(II) (FP) or without activation (SP) was also tested. Kinetic oxidation of PAHs was tracked in spiked sand and in aged PAH contaminated soils at circumneutral pH. Quartz sand was spiked with: (i) single model pollutant (fluorenone) and (ii) organic extract isolated from two PAH contaminated soils (H and NM sampled from ancient coking plants) and was subjected to oxidation. Oxidation was also performed on real H and NM soils with and without an extraction pretreatment. Results indicate that oxidation of fluorenone resulted in its complete degradation by AP while abatement was very low (<20%) by SP or FP. In soil extracts spiked on sand, significant degradation of 16 PAHs was observed by AP (70-80%) in 1 week as compared to only 15% by SP or FP systems. But no PAH abatement was observed in real soils whatever the treatment used (AP, FP or SP). Then soils were subjected to an extraction pretreatment but without isolation of organic extract from soil. Oxidation of this pretreated soil showed significant abatement of PAHs by AP. On the other hand, very low degradation was achieved by FP or SP. Selective degradation of PAHs was observed by AP with lower degradation efficiency towards high molecular weight PAHs. Analyses revealed that no by-products were formed during oxidation. The results of this study demonstrate that magnetite can activate persulfate at circumneutral pH for an effective degradation of PAHs in soils. However, availability of PAHs and soil matrix were found to be the most critical factors for degradation efficiency.     

Removal of polycyclic aromatic hydrocarbons from manufactured gas plant-contaminated soils using sunflower oil: laboratory column experiments

Laboratory column experiments were performed to remove PAHs (polycyclic aromatic hydrocarbons) from two contaminated soils using sunflower oil. Two liters of sunflower oil was added to the top of the columns (33 cm x 21 cm) packed with 1 kg of PAH-contaminated soil. The sunflower oil was applied sequentially in two different ways, i.e. five additions of 400 ml or two additions of 1l. The influence of PAH concentration and the volume of sunflower oil on PAH removal were examined. A soil respiration experiment was carried out and organic carbon contents of the soils were measured to determine degradability of remaining sunflower oil in the soils. Results showed that the sunflower oil was effective in removing PAHs from the two soils, more PAHs were removed by adding sunflower oil in two steps than in five steps, probably because of the slower flow rate in the former method. More than 90% of total PAHs was removed from a heavily contaminated soil (with a total 13 PAH concentration of 4721 mg kg(-1)) using 4 l of sunflower oil. A similar removal efficiency was obtained for another contaminated soil (with a total 13 PAH concentration of 724 mg kg(-1)), while only 2l was needed to give a similar efficiency. Approximately 4-5% of the sunflower oil remained in the soils. Soil respiration curves showed that remaining sunflower oil was degraded by allowing air exchange and supplying with nutrients. Organic carbon content of the soil was restored to original level after 180 d incubation. These results indicated that the sunflower oil had a great capacity to remove PAHs from contaminated soils, and sunflower oil solubilization can be an alternative technique for remediation of PAH contaminated soils.     

Phytoremediation of mixed-contaminated soil using the hyperaccumulator plant Alyssum lesbiacum: evidence of histidine as a measure of phytoextractable nickel

In this study we examine the effects of polycyclic aromatic hydrocarbons (PAHs) on the ability of the hyperaccumulator plant Alyssum lesbiacum to phytoextract nickel from co-contaminated soil. Planted and unplanted mesocosms containing the contaminated soils were repeatedly amended with sorbitan trioleate, salicylic acid and histidine in various combinations to enhance the degradation of two PAHs (phenanthrene and chrysene) and increase nickel phytoextraction. Plant growth was negatively affected by PAHs; however, there was no significant effect on the phytoextraction of Ni per unit biomass of shoot. Exogenous histidine did not increase nickel phytoextraction, but the histidine-extractable fraction of soil nickel showed a high correlation with phytoextractable nickel. These results indicate that Alyssum lesbiacum might be effective in phytoextracting nickel from marginally PAH-contaminated soils. In addition, we provide evidence for the broader applicability of histidine for quantifying and predicting Ni phytoavailability in soils.     

Residue level of polycyclic aromatic hydrocarbons in Japanese paddy soils from 1959 to 2002

The residue level of 21 polycyclic aromatic hydrocarbons (PAHs) and the temporal changes in this level were investigated in paddy soils collected from particular experimental sites in Japan from 1959 to 2002. The average total PAH concentration in all the samples was 496 microg kg(-1), and it ranged from 52.9 to 2180 microg kg(-1). The residue level of the PAHs was the highest during the 1960s, rapidly decreased during the 1970s, and remained almost constant thereafter. Relatively high PAH concentrations were observed in soils from areas that experienced heavy snowfall and that had relatively low air temperature. The predominant PAHs were phenanthrene, fluoranthene, naphthalene, and pyrene, and their concentration overall and in relation to that of the total PAHs decreased each year since the 1960s. Similarities in the PAH profiles among the locations were determined using the concentration correlation matrix and cluster analysis, and ratios of the levels of specific PAH pairs were also calculated to determine their origin. The collected data suggested that the origins of soil PAHs changed chronologically from the burning of agricultural wastes such as stubble before the mid-1970s to the combustion of fossil fuel and its secondary products after the mid-1970s.